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4D scanning transmission electron microscopy (4D-STEM) reveals crystallization mechanisms of organic semiconductors on graphene

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Abstract

Organic semiconductor materials exhibit properties that enable use in various electrical devices, such as organic solar cells and field-effect transistors. It is challenging, however, to control molecular packing at organic–organic interfaces and also characterize the morphology at buried interlayers. Here, we demonstrate via vertical physical vapor transport the ability to grow single-crystalline bilayer organic semiconductors on graphene using two small molecules: zinc phthalocyanine (ZnPc), and 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA). We employ 4D-scanning transmission electron diffraction (4D-STEM) to directly observe the orientation distribution of ZnPc and PTCDA crystallites on graphene, explaining the different growth mechanisms of organic molecules on graphene substrates, and we predict the morphology of the stacked ZnPc/PTCDA heterojunctions.

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Analyzed and raw data relevant to this study are available from the corresponding authors upon reasonable requests.

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Acknowledgments

Funding from the Center for Self-Assembled Organic Electronics and the Office of Naval Research under Award N00014-19-1-2453 is acknowledged. Funding is also acknowledged from ARL (US Army)/Design and Synthesis of Materials for Agile Manufacturing under Award 19040007-AWD, with Subaward Number 10730-GR/10747-GR.

Funding

The 4D-STEM work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The X-ray work is based on research conducted at the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

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Authors and Affiliations

  1. Department of Chemistry, The Pennsylvania State University, University Park, State College, PA, 16802, USA

    Zixuan Guo

  2. National Center for Electron Microscopy, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    Colin Ophus & Karen C. Bustillo

  3. Department of Materials Science and Engineering, The Pennsylvania State University, University Park, State College, PA, 16802, USA

    Ryan Fair & Enrique D. Gomez

  4. Center for Advancing Electronics Dresden, Department of Electrical and Computer Engineering, University of Technology Dresden, 01069, Dresden, Germany

    Stefan C. B. Mannsfeld

  5. Department of Chemistry, Naval Air Warfare Center Weapons Division, China Lake, CA, 93555, USA

    Alejandro L. Briseno

  6. Department of Chemical Engineering, The Pennsylvania State University, University Park, State College, PA, 16802, USA

    Enrique D. Gomez

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  1. Zixuan Guo
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Correspondence to Alejandro L. Briseno or Enrique D. Gomez.

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Guo, Z., Ophus, C., Bustillo, K.C. et al. 4D scanning transmission electron microscopy (4D-STEM) reveals crystallization mechanisms of organic semiconductors on graphene. MRS Communications 13, 47–54 (2023). https://doi.org/10.1557/s43579-022-00310-5

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