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Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films

Nature Materials volume 8, pages 952–958 (2009)Cite this article

Abstract

Solution-processable organic semiconductors are central to developing viable printed electronics, and performance comparable to that of amorphous silicon has been reported for films grown from soluble semiconductors. However, the seemingly desirable formation of large crystalline domains introduces grain boundaries, resulting in substantial device-to-device performance variations. Indeed, for films where the grain-boundary structure is random, a few unfavourable grain boundaries may dominate device performance. Here we isolate the effects of molecular-level structure at grain boundaries by engineering the microstructure of the high-performance n-type perylenediimide semiconductor PDI8–CN2 and analyse their consequences for charge transport. A combination of advanced X-ray scattering, first-principles computation and transistor characterization applied to PDI8–CN2 films reveals that grain-boundary orientation modulates carrier mobility by approximately two orders of magnitude. For PDI8–CN2 we show that the molecular packing motif (that is, herringbone versus slip-stacked) plays a decisive part in grain-boundary-induced transport anisotropy. The results of this study provide important guidelines for designing device-optimized molecular semiconductors.

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Figure 1: Aligned films of the n-type small-molecule semiconductor PDI8–CN2.
Figure 2: Molecular packing in aligned PDI8–CN2 thin films.
Figure 3: Phi-scan analysis of PDI8–CN2 growth anisotropy.
Figure 4: Mobility and activation-energy anisotropy for PDI8–CN2 films.
Figure 5: In-plane grain boundaries in small-molecule films.

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Acknowledgements

Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the US DOE, Office of Basic Energy Sciences. J.R. gratefully acknowledges financial support from ONR in the form of an NDSEG Fellowship, and A.S. and L.H.J. gratefully acknowledge financial support from NSF in the form of, respectively, a Career Award and a Graduate Student Fellowship. This publication was partially based on work supported by the Center for Advanced Molecular Photovoltaics (Award No KUS-C1-015-21, made by King Abdullah University of Science and Technology, KAUST). J.E.N. thanks AFOSR (FA9550-09-1-0436), and T.J.M. and A.F. thank AFOSR (FA9550-08-1-0331) for support of this research.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA

    Jonathan Rivnay, Leslie H. Jimison & Alberto Salleo

  2. Palo Alto Research Center (PARC), Palo Alto, California 94304, USA

    John E. Northrup

  3. Stanford Synchrotron Radiation Lightsource, Menlo Park, California 94025, USA

    Michael F. Toney

  4. Department of Applied Physics, Stanford University, Stanford, California 94305, USA

    Rodrigo Noriega

  5. Polyera Corporation, Skokie, Illinois 60077, USA

    Shaofeng Lu & Antonio Facchetti

  6. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA

    Tobin J. Marks & Antonio Facchetti

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  1. Jonathan Rivnay
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Contributions

J.R. and A.S. conceived and designed the research. J.R. fabricated films/devices, and carried out electrical testing. J.R., L.H.J., R.N. and M.F.T. carried out X-ray-scattering experiments and unit-cell determination. J.E.N. carried out first-principles calculations. T.J.M. and A.F. oversaw materials design, synthesis and processing. S.L. synthesized the material. J.R., J.E.N. and A.S. prepared the manuscript. All authors revised and approved the manuscript.

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Correspondence to Alberto Salleo.

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Rivnay, J., Jimison, L., Northrup, J. et al. Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films. Nature Mater 8, 952–958 (2009). https://doi.org/10.1038/nmat2570

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