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Asymmetric dyes align inside carbon nanotubes to yield a large nonlinear optical response

Nature Nanotechnology volume 10, pages 248–252 (2015)Cite this article

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Abstract

Asymmetric dye molecules have unusual optical and electronic properties1,2,3. For instance, they show a strong second-order nonlinear optical (NLO) response that has attracted great interest for potential applications in electro-optic modulators for optical telecommunications and in wavelength conversion of lasers2,3. However, the strong Coulombic interaction between the large dipole moments of these molecules favours a pairwise antiparallel alignment that cancels out the NLO response when incorporated into bulk materials. Here, we show that by including an elongated dipolar dye (p,p′-dimethylaminonitrostilbene, DANS, a prototypical asymmetric dye with a strong NLO response4) inside single-walled carbon nanotubes (SWCNTs)5,6, an ideal head-to-tail alignment in which all electric dipoles point in the same sense is naturally created. We have applied this concept to synthesize solution-processible DANS-filled SWCNTs that show an extremely large total dipole moment and static hyperpolarizability (β0 = 9,800 × 10−30 e.s.u.), resulting from the coherent alignment of arrays of ∼70 DANS molecules.

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Figure 1: Stacking of dipolar molecules in different dimensions.
Figure 2: Absorption and PLE spectroscopy.
Figure 3: Raman and PLE shifts showing the critical diameter for DANS encapsulation.
Figure 4: Wavelength-dependent NLO polarizability.

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Acknowledgements

The authors thank W. Van Werveke for preliminary work indicating a similar alignment with a different NLO chromophore (Disperse Red 1). Financial support from the Fund for Scientific Research – Flanders (FWO) for the SWCNT work (projects G040011N, G021112N and 1513513N) and for the NLO measurements (projects G.0129.07, G.0206.12, 1523913N and G.0522.13N) is acknowledged. Part of this work was supported by a UA-NOI-BOF grant, the Hercules Foundation, and EU ITN Nano2Fun. S.C. and J.C. are postdoctoral fellows of the FWO.

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Author notes

  1. Sofie Cambré and Jochen Campo: These authors contributed equally to this work

Authors and Affiliations

  1. Physics Department, University of Antwerp, Universiteitsplein 1, Antwerp, B-2610, Belgium

    Sofie Cambré, Jochen Campo, Charlie Beirnaert, Christof Verlackt & Wim Wenseleers

  2. Chemistry Department, Laboratory of Adsorption and Catalysis, University of Antwerp, Universiteitsplein 1, Antwerp, B-2610, Belgium

    Pegie Cool

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Contributions

S.C. performed most of the synthesis and designed and performed most Raman and PLE experiments. J.C. designed and performed the HRS experiments and some synthesis. C.B. conducted part of the initial synthesis and spectroscopic characterization of DANS@oARC samples. C.V. independently reproduced the synthesis for the HiPco samples and part of the spectroscopic characterization. P.C. performed the thermogravimetric analysis. W.W. conceived the idea and co-designed and supervised all experiments. All authors contributed to writing the manuscript.

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Correspondence to Wim Wenseleers.

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The authors declare no competing financial interests.

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Cambré, S., Campo, J., Beirnaert, C. et al. Asymmetric dyes align inside carbon nanotubes to yield a large nonlinear optical response. Nature Nanotech 10, 248–252 (2015). https://doi.org/10.1038/nnano.2015.1

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