Supramolecular organic nanowires are ideal nanostructures for optoelectronics because they exhibit both efficient exciton generation as a result of their high absorption coefficient and remarkable light sensitivity due to the low number of grain boundaries and high surface-to-volume ratio. To harvest photocurrent directly from supramolecular nanowires it is necessary to wire them up with nanoelectrodes that possess different work functions. However, devising strategies that can connect multiple nanowires at the same time has been challenging. Here, we report a general approach to simultaneously integrate hundreds of supramolecular nanowires of N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) in a hexagonal nanomesh scaffold with asymmetric nanoelectrodes. Optimized PTCDI-C8 nanowire photovoltaic devices exhibit a signal-to-noise ratio approaching 107, a photoresponse time as fast as 10 ns and an external quantum efficiency >55%. This nanomesh scaffold can also be used to investigate the fundamental mechanism of photoelectrical conversion in other low-dimensional semiconducting nanostructures.
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Hoeben, F. J. M., Jonkheijm, P., Meijer, E. W. & Schenning, A. About supramolecular assemblies of π-conjugated systems. Chem. Rev. 105, 1491–1546 (2005).
Lee, C. C., Grenier, C., Meijer, E. W. & Schenning, A. Preparation and characterization of helical self-assembled nanofibers. Chem. Soc. Rev. 38, 671–683 (2009).
Chen, Z. J., Lohr, A., Saha-Moller, C. R. & Wurthner, F. Self-assembled π-stacks of functional dyes in solution: structural and thermodynamic features. Chem. Soc. Rev. 38, 564–584 (2009).
Jain, A. & George, S. J. New directions in supramolecular electronics. Mater. Today 18, 206–214 (2015).
Jiang, L., Fu, Y., Li, H. & Hu, W. Single-crystalline, size, and orientation controllable nanowires and ultralong microwires of organic semiconductor with strong photoswitching property. J. Am. Chem. Soc. 130, 3937–3941 (2008).
Marty, R. et al. Hierarchically structured microfibers of “single stack” perylene bisimide and quaterthiophene nanowires. ACS Nano 7, 8498–8508 (2013).
Wei, L., Yao, J. N. & Fu, H. B. Solvent-assisted self-assembly of fullerene into single-crystal ultrathin microribbons as highly sensitive UV-visible photodetectors. ACS Nano 7, 7573–7582 (2013).
Wicklein, A., Ghosh, S., Sommer, M., Würthner, F. & Thelakkat, M. Self-assembly of semiconductor organogelator nanowires for photoinduced charge separation. ACS Nano 3, 1107–1114 (2009).
Che, Y. et al. Interfacial engineering of organic nanofibril heterojunctions into highly photoconductive materials. J. Am. Chem. Soc. 133, 1087–1091 (2011).
Tian, B. Z. et al. Coaxial silicon nanowires as solar cells and nanoelectronic power sources. Nature 449, 885–890 (2007).
Haedler, A. T. et al. Long-range energy transport in single supramolecular nanofibres at room temperature. Nature 523, 196–199 (2015).
Garnett, E. & Yang, P. D. Light trapping in silicon nanowire solar cells. Nano Lett. 10, 1082–1087 (2010).
Briseno, A. L. et al. Fabrication of field-effect transistors from hexathiapentacene single-crystal nanowires. Nano Lett. 7, 668–675 (2007).
Briseno, A. L. et al. Perylenediimide nanowires and their use in fabricating field-effect transistors and complementary inverters. Nano Lett. 7, 2847–2853 (2007).
An, B. K., Gierschner, J. & Park, S. Y. π-Conjugated cyanostilbene derivatives: a unique self-assembly motif for molecular nanostructures with enhanced emission and transport. Accounts Chem. Res. 45, 544–554 (2012).
Walker, B. J., Dorn, A., Bulovic, V. & Bawendi, M. G. Color-selective photocurrent enhancement in coupled J-aggregate/nanowires formed in solution. Nano Lett. 11, 2655–2659 (2011).
Bredas, J. L., Norton, J. E., Cornil, J. & Coropceanu, V. Molecular understanding of organic solar cells: the challenges. Accounts Chem. Res. 42, 1691–1699 (2009).
Wurthner, F. & Meerholz, K. Systems chemistry approach in organic photovoltaics. Chem. Eur. J. 16, 9366–9373 (2010).
Palmer, L. C. & Stupp, S. I. Molecular self-assembly into one-dimensional nanostructures. Accounts Chem. Res. 41, 1674–1684 (2008).
Shao, H., Nguyen, T., Romano, N. C., Modarelli, D. A. & Parquette, J. R. Self-assembly of 1-D n-type nanostructures based on naphthalene diimide-appended dipeptides. J. Am. Chem. Soc. 131, 16374–16376 (2009).
Balakrishnan, K. et al. Nanobelt self-assembly from an organic n-type semiconductor: propoxyethyl-PTCDI. J. Am. Chem. Soc. 127, 10496–10497 (2005).
Tovar, J. D. Supramolecular construction of optoelectronic biomaterials. Acc. Chem. Res. 46, 1527–1537 (2013).
Babu, S. S., Praveen, V. K. & Ajayaghosh, A. Functional π-gelators and their applications. Chem. Rev. 114, 1973–2129 (2014).
Gorl, D., Zhang, X., Stepanenko, V. & Wurthner, F. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides. Nature Commun. 6, 7006 (2015).
Gemayel, M. E. et al. Tuning the photoresponse in organic field-effect transistors. J. Am. Chem. Soc. 134, 2429–2433 (2012).
Sagade, A. A. et al. High-mobility field effect transistors based on supramolecular charge transfer nanofibres. Adv. Mater. 25, 559–564 (2013).
Hollamby, M. J. et al. Directed assembly of optoelectronically active alkyl-π-conjugated molecules by adding n-alkanes or π-conjugated species. Nature Chem. 6, 690–696 (2014).
Zhang, Y. et al. Organic single-crystalline p−n junction nanoribbons. J. Am. Chem. Soc. 132, 11580–11584 (2010).
Cui, Q. H. et al. Coaxial organic p-n heterojunction nanowire arrays: one-step synthesis and photoelectric properties. Adv. Mater. 24, 2332–2336 (2012).
Zhang, W. et al. Supramolecular linear heterojunction composed of graphite-like semiconducting nanotubular segments. Science 334, 340–343 (2011).
Faramarzi, V. et al. Light-triggered self-construction of supramolecular organic nanowires as metallic interconnects. Nature Chem. 4, 485–490 (2012).
Moulin, E., Cid, J. J. & Giuseppone, N. Advances in supramolecular electronics - from randomly self-assembled nanostructures to addressable self-organized interconnects. Adv. Mater. 25, 477–487 (2013).
Kim, B. J., Yu, H., Oh, J. H., Kang, M. S. & Cho, J. H. Electrical transport through single nanowires of dialkyl perylene diimide. J. Phys. Chem. C 117, 10743–10749 (2013).
Hulteen, J. C. & Vanduyne, R. P. Nanosphere lithography: a materials general fabrication process for periodic particle array surfaces. J. Vac. Sci. Technol. A 13, 1553–1558 (1995).
Sinitskii, A. & Tour, J. M. Patterning graphene through the self-assembled templates: toward periodic two-dimensional graphene nanostructures with semiconductor properties. J. Am. Chem. Soc. 132, 14730–14732 (2010).
Gao, T. C., Wang, B. M., Ding, B., Lee, J. K. & Leu, P. W. Uniform and ordered copper nanomeshes by microsphere lithography for transparent electrodes. Nano Lett. 14, 2105–2110 (2014).
Gao, P. Q. et al. Large-area nanosphere self-assembly by a micro-propulsive injection method for high throughput periodic surface nanotexturing. Nano Lett. 15, 4591–4598 (2015).
Bao, Z. et al. Toward controllable self-assembly of microstructures: selective functionalization and fabrication of patterned spheres. Chem. Mater. 14, 24–26 (2002).
Cao, Q. et al. Arrays of single-walled carbon nanotubes with full surface coverage for high-performance electronics. Nature Nanotech. 8, 180–186 (2013).
Dintinger, J., Klein, S. & Ebbesen, T. W. Molecule-surface plasmon interactions in hole arrays: enhanced absorption, refractive index changes, and all-optical switching. Adv. Mater. 18, 1267–1270 (2006).
Parker, I. D. & Kim, H. H. Fabrication of polymer light-emitting-diodes using doped silicon electrodes. Appl. Phys. Lett. 64, 1774–1776 (1994).
Baeg, K. J., Binda, M., Natali, D., Caironi, M. & Noh, Y. Y. Organic light detectors: photodiodes and phototransistors. Adv. Mater. 25, 4267–4295 (2013).
Yu, H., Bao, Z. A. & Oh, J. H. High-performance phototransistors based on single-crystalline n-channel organic nanowires and photogenerated charge-carrier behaviors. Adv. Funct. Mater. 23, 629–639 (2013).
Levermore, P. A., Jin, R., Wang, X. H., de Mello, J. C. & Bradley, D. D. C. Organic light-emitting diodes based on poly(9,9-dioctylfluorene-co-bithiophene) (F8T2). Adv. Funct. Mater. 19, 950–957 (2009).
Lei, T., Dou, J. H. & Pei, J. Influence of alkyl chain branching positions on the hole mobilities of polymer thin-film transistors. Adv. Mater. 24, 6457–6461 (2012).
Li, Y. F. Molecular design of photovoltaic materials for polymer solar cells: toward suitable electronic energy levels and broad absorption. Accounts Chem. Res. 45, 723–733 (2012).
Shaw, P. E., Ruseckas, A. & Samuel, I. D. W. Exciton diffusion measurements in poly(3-hexylthiophene). Adv. Mater. 20, 3516–3520 (2008).
Najafov, H., Lee, B., Zhou, Q., Feldman, L. C. & Podzorov, V. Observation of long-range exciton diffusion in highly ordered organic semiconductors. Nature Mater. 9, 938–943 (2010).
Pinto, R. M. et al. Effect of molecular stacking on exciton diffusion in crystalline organic semiconductors. J. Am. Chem. Soc. 137, 7104–7110 (2015).
Sung, J., Kim, P., Fimmel, B., Wurthner, F. & Kim, D. Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides. Nature Commun. 6, 8646 (2015).
We thank F. Liscio for help with XRD analysis. This work was financially supported by European Commission through the European Research Council project SUPRAFUNCTION (grant agreement no. 257305) and the Marie Curie ITN project iSwitch (grant agreement no. 642196), the ANR Equipex Union (ANR-10-EQPX-52-01), the Labex projects CSC (ANR-10-LABX-0026 CSC) and Nanostructures in Interaction with their Environment (ANR-11-LABX-0058 NIE) within the Investissement d'Avenir program (ANR-10- 120 IDEX-0002-02), and the International Center for Frontier Research in Chemistry (icFRC).
The authors declare no competing financial interests.
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Zhang, L., Zhong, X., Pavlica, E. et al. A nanomesh scaffold for supramolecular nanowire optoelectronic devices. Nature Nanotech 11, 900–906 (2016). https://doi.org/10.1038/nnano.2016.125
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