Abstract
The sensitive response of the nematic graphene oxide (GO) phase to external stimuli makes this phase attractive for extending the applicability of GO and reduced GO to solution processes and electro-optic devices. However, contrary to expectations, the alignment of nematic GO has been difficult to control through the application of electric fields or surface treatments. Here, we show that when interflake interactions are sufficiently weak, both the degree of microscopic ordering and the direction of macroscopic alignment of GO liquid crystals (LCs) can be readily controlled by applying low electric fields. We also show that the large polarizability anisotropy of GO and Onsager excluded-volume effect cooperatively give rise to Kerr coefficients that are about three orders of magnitude larger than the maximum value obtained so far in molecular LCs. The extremely large Kerr coefficient allowed us to fabricate electro-optic devices with macroscopic electrodes, as well as well-aligned, defect-free GO over wide areas.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Zakri, C. et al. Liquid crystals of carbon nanotubes and graphene. Phil. Trans. R. Soc. A 371, 20120499 (2013).
Hernandez, Y. et al. High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotech. 3, 563–568 (2008).
Eda, G., Fanchini, G. & Chhowalla, M. Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. Nature Nanotech. 3, 270–274 (2008).
Loh, K. P., Bao, Q., Eda, G. & Chhowalla, M. Graphene oxide as a chemically tunable platform for optical applications. Nature Chem. 2, 1015–1024 (2010).
Behabtu, N. et al. Spontaneous high-concentration dispersions and liquid crystals of graphene. Nature Nanotech. 5, 406–411 (2010).
Williams, G., Seger, B. & Kamat, P. V. TiO2-graphene nanocomposites UV-assisted photocatalytic reduction of graphene oxide. ACS Nano 2, 1487–1491 (2008).
Dreyer, D. R., Park, S., Bielawski, C. W. & Ruoff, R. S. The chemistry of graphene oxide. Chem. Soc. Rev. 39, 228–240 (2010).
Demus, D., Goodby, J. W., Gray, G. W. & Spiess, H-W. Handbook of Liquid Crystals Vol 1 (Wiley-VCH, (1998).
Hisakado, Y., Kikuchi, H., Nagamura, T. & Kajiyama, T. Large electro-optic Kerr effect in polymer stabilised liquid-crystalline blue phases. Adv. Mater. 17, 96–98 (2005).
Kim, J. E. et al. Graphene oxide liquid crystals. Angew. Chem. Int. Ed. 50, 3043–3047 (2011).
Dan, B. et al. Liquid crystals of aqueous, giant graphene oxide flakes. Soft. Matter. 7, 11154–11159 (2011).
Dierking, I., Scalia, G. & Morales, P. Liquid crystal–carbon nanotube dispersions. J. Appl. Phys 97, 044309 (2005).
Dierking, I., Scalia, G., Morales, P. & LeClere, D. Aligning and reorienting carbon nanotubes with nematic liquid crystals. Adv. Mater. 16, 865–869 (2004).
Tie, W. et al. Dynamic electro-optic response of graphene/graphitic flakes in nematic liquid crystals. Opt. Express 21, 19867–19879 (2013).
Onsager, L. The effects of shape on the interaction of colloidal particles. Ann. NY Acad. Sci. 51, 627–659 (1949).
Bates, M. A. & Frenkel, D. Nematic–isotropic transition in polydisperse systems of infinitely thin hard platelets. J. Chem. Phys. 110, 6553–6559 (1999).
Zhang, S. & Kumar, S. Carbon nanotubes as liquid crystals. Small 4, 1270–1283 (2008).
Xu, Z. & Gao, C. Aqueous liquid crystals of graphene oxide. ACS Nano 5, 2908–2915 (2011).
Davis, V. A. et al. Phase behavior and rheology of SWNTs in superacids. Macromolecules 37, 154–160 (2004).
Hummers, W. S. & Offema, R. E. Preparation of graphite oxide. J. Am. Chem. Soc. 80, 1339 (1958).
Hontoria-Lucas, C., Lopez-Peinado, A. J., Lopez-Gonzalez, J. de D., Rojas-Cervantes, M. L. & Martin-Aranda, R. M. Study of oxygen-containing groups in a series of graphite oxides: physical and chemical characterization. Carbon 33, 1585–1592 (1995).
Aboutalebi, S. H., Gudarzi, M. M., Zheng, Q. B. & Kim, J-K. Spontaneous formation of liquid crystals in ultralarge graphene oxide dispersions. Adv. Funct. Mater. 21, 2978–2988 (2011).
Chen, K-M., Gauza, S., Xianyu, H. & Wu, S-T. Hysteresis effects in blue-phase liquid crystals. J. Disp. Technol. 6, 318–322 (2010).
Rao, L. et al. Critical field for a hysteresis-free BPLC device. J. Disp. Technol. 7, 627–629 (2011).
Jimenez, M. L., Fornasari, L., Mantegazza, F., Mourad, M. C. & Bellini, T. Electric birefringence of dispersions of platelets. Langmuir 28, 251–258 (2012).
Mohapatra, A. K., Bason, M. G., Butscher, B., Weatherill, K. J. & Adams, C. S. A giant electro-optic effect using polarizable dark states. Nature Phys. 4, 890–894 (2008).
Haseba, Y., Kikuchi, H., Nagamura, T. & Kajiyama, T. Large electro-optic Kerr effect in nanostructured chiral liquid-crystal composites over a wide temperature range. Adv. Mater. 17, 2311–2315 (2005).
Chen, Y., Xu, D., Wu, S-T., Yamamoto, S-I. & Haseba, Y. A low voltage and submillisecond-response polymer-stabilized blue phase liquid crystal. Appl. Phys. Lett. 102, 141116 (2013).
Dimiev, A. M., Alemany, L. B. & Tour, J. M. Graphene oxide origin of acidity, its instability in water and a new dynamic structural model. ACS Nano. 7, 576–588 (2013).
O’Konski, C. T. Electric properties of macromolecules. V. Theory of ionic polarization in polyelectrolytes. J. Phys. Chem. 64, 605–619 (1960).
Dozov, I. et al. Electric-field-induced perfect anti-nematic order in isotropic aqueous suspensions of a natural beidellite clay. J. Phys. Chem. B 115, 7751–7765 (2011).
Straley, J. P. The gas of long rods as a model for lyotropic liquid crystals. Mol. Cryst. Liq. Cryst. 22, 333–357 (1973).
Van der Beek, D. et al. Magnetic-field-induced orientational order in the isotropic phase of hard colloidal platelets. Phys. Rev. E 73, 041402 (2006).
Acknowledgements
This work was supported by the National Research Foundation of Korea (NRF) grants funded by the Korea government (MSIP) (No. 2012R1A1A1012167 and No. 2013R1A1A2057455).
Author information
Authors and Affiliations
Contributions
J-K.S. planned and supervised the project. T-Z.S. and S-H.H. carried out all the experiments. All authors analysed the data and participated in writing the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary Information
Supplementary Information (PDF 2253 kb)
Supplementary Information
Supplementary Movie S1 (MP4 2546 kb)
Rights and permissions
About this article
Cite this article
Shen, TZ., Hong, SH. & Song, JK. Electro-optical switching of graphene oxide liquid crystals with an extremely large Kerr coefficient. Nature Mater 13, 394–399 (2014). https://doi.org/10.1038/nmat3888
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nmat3888
This article is cited by
-
Graphene oxide for photonics, electronics and optoelectronics
Nature Reviews Chemistry (2023)
-
Deep ultraviolet hydrogel based on 2D cobalt-doped titanate
Light: Science & Applications (2023)
-
Liquid crystalline 2D borophene oxide for inorganic optical devices
Nature Communications (2022)
-
Magnetically tunable and stable deep-ultraviolet birefringent optics using two-dimensional hexagonal boron nitride
Nature Nanotechnology (2022)
-
A 2D material–based transparent hydrogel with engineerable interference colours
Nature Communications (2022)