Unveiling Electronic Properties in Metal-Phthalocyanine-based Py-razine-linked Conjugated Two-Dimensional Covalent-Organic Frameworks
Posted on 2019-09-18 - 08:25 authored by Hung-Hsuan Lin
pi-Conjugated two-dimensional
covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive
materials for (opto-)electronic and chemiresistive sensing applications.
However, understanding the intricate interplay between chemistry, structure and
conductivity in pi-conjugated 2D
COFs remains elusive. Here, we report a detailed characterization 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 density 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 anisotropic, with hole mobilities being
practically null in-plane and finite out-of-plane for these 2D COFs.
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Wang, Mingchao; Ballabio, Marco; Wang, Mao; Lin, Hung-Hsuan; Biswal, Bishnu P.; Han, Xiaocang; et al. (2019). Unveiling Electronic Properties in Metal-Phthalocyanine-based Py-razine-linked Conjugated Two-Dimensional Covalent-Organic Frameworks. figshare. Collection. https://doi.org/10.6084/m9.figshare.c.4669574.v1
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FUNDING
EU Graphene Flagship, ERC Consolidator Grant (T2DCP)
Coordination Networks: Building Blocks for Functional Sys-tems (SPP 1928, COORNET)
German Science Council, Center of Advancing Electronics Dresden, EXC1056, (cfaed) and OR 349/1
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AUTHORS (16)
MW
Mingchao Wang
MB
Marco Ballabio
MW
Mao Wang
BB
Bishnu P. Biswal
XH
Xiaocang Han
SP
Silvia Paasch
EB
Eike Brunner
PL
Pan Liu
MC
Mingwei Chen
MB
Mischa Bonn
TH
Thomas Heine
SZ
Shengqiang Zhou
EC
Enrique Cánovas
RD
Renhao Dong
XF
Xinliang Feng