Electronic Properties of Metal-Phthalocyanine-Based 2D conjugated COFs
Mingchao Wang a, Shengqiang Zhou b, Mischa Bonn c, Thomas Heine a, Enrique Cánovas c d, Renhao Dong a, Xinliang Feng a
a Technische Universität Dresden, Hallwachsstraße, 3, Dresden, Germany
b Helmholtz-Zentrum Dresden-Rossendorf, PO Box 510119, Dresden, 01314, Germany
c Max Planck Institute for polymer Research, 55128 Mainz, Germany
d Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia), c/Faraday 9, Cantoblanco, 28049, Madrid
Proceedings of Organic 2D Crystalline Materials: Chemistry, Physics and Devices (O2DMAT)
Madrid, Spain, 2022 September 15th - 16th
Organizers: Enrique Cánovas, Renhao Dong and Hai Wang
Contributed talk, Mingchao Wang, presentation 016
Publication date: 11th July 2022

Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are emerging as a unique class of semiconducting 2D polymers for (opto-)electronics and energy devices. However, understanding the intricate interplay between the chemical structure and charge transport remains a challenge.[1,2] We have demonstrated two metal−phthalocyanine-based pyrazine-linked 2D c-COFs (termed as MPc-pz COF, M = Cu or Zn) as p-type semiconductors with a band gap of ∼1.2 eV and intrinsic charge mobility up to ∼5 cm2/(Vs).[3] The combination of Hall effect measurements, Terahertz spectroscopy, and density functional theory calculated electronic band structures provide a rational approach on how to assess structure-/doping-electronic property relationships.[2,3] The results reveal that varying metal center from Cu to Zn has a negligible effect on the charge transport behaviors. After reversible p-type doping with I2, the doping-defined 2D c-COF displays enhanced conductivity by 3 orders of magnitude, due to the elevated carrier concentration.[4] Remarkably, charge mobility also increased upon doping, which can be traced to increased scattering time for free charge carriers, indicating that scattering mechanisms limiting the mobility are mitigated by doping. These works provide a guideline on how to assess the structure-electronic property relationships in 2D c-COFs semiconductors and highlight their potential in organic (opto-)electronic devices.

We thank the financial support from ERC Grants (T2DCP and FC2DMOF), EU Graphene Flagship, DFG project (CRC 1415), and Center for Advancing Electronics Dresden.

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