Unveiling Electronic Properties in Metal–Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks

Autor: Wang, Mingchao, Ballabio, Marco, Wang, Mao, Lin, Hung-Hsuan, Biswal, Bishnu P., Han, Xiaocang, Paasch, Silvia, Brunner, Eike, Liu, Pan, Chen, Mingwei, Bonn, Mischa, Heine, Thomas, Zhou, Shengqiang, Cánovas, Enrique, Dong, Renhao, Feng, Xinliang
Jazyk: angličtina
Rok vydání: 2019
Předmět:
Druh dokumentu: Článek
ISSN: 1520-5126
DOI: 10.1021/jacs.9b07644
Popis: π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electro-active materials for (opto-)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed charac-terization for the electronic properties of two novel samples consisting of Zn- and Cu-phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal-phthalocyanine (M=Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ~1.2 eV. Mobilities up to ~5 cm²/Vs are resolved in the dc limit, which represent a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall Effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with den-sity functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (~5×10⁻⁷ S/cm), charge carrier density (~10¹² cm⁻³), charge carrier scattering rate (~3×10¹³ s⁻¹), and effective mass (~2.3m₀) of majority carriers (holes). Notably, charge carrier transport is found to be aniso-tropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.
Databáze: Networked Digital Library of Theses & Dissertations