(Invited) Record-High Charge Carrier Mobilities in 2D Covalent- and Metal- Organic Frameworks
Authors: Cánovas Enrique 
Published: September 2023

Organic based 2D layered materials (2DLMs) including 2D covalent and metal organic frameworks (COFs and MOFs) are promising candidates for traditional applications in gas storage and separation as well as catalysis. This is due to the long-range crystalline order that can be achieved in them as well as their tunable porosity and chemistry. Synthetic chemistry efforts aiming an enhanced coupling between their building block constituents have recently led to the design of (semi-)conducting MOFs and COFs displaying high conductivities and record charge carrier mobilities. These achievements have opened the path for their application in opto-electronics. Yet, despite being a critical aspect for the development of 2DLM based electronics, understanding the true nature of charge transport in these novel materials by stabilising reliable structure-property-function relations is largely unexplored.

Here I will present time-resolved high-frequency (terahertz) conductivity studies of state-of-the-art organic based 2DLMs materials revealing semiconducting behaviour and record charge carrier mobilities. First, I will present a detailed characterization for the electronic properties of Zn– and Cu–phthalocyanine-based pyrazine-linked 2D COFs [1,2]. These 2D COFs, synthesized by condensation of metal–phthalocyanine (M = Zn and Cu) and pyrene derivatives, are obtained as polycrystalline-layered semiconductors displaying p-type doping and a band gap of ∼1.2 eV. 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). However, both samples reveal slightly different mobilities that can be attributed to charge carrier localization at crystalline grain boundaries. Furthermore we analyse the effect of iodine doping on the Zn based 2D COFs. The resultant 2D c-COF ZnPc-pz-I2 maintains its structural integrity and displays enhanced conductivity by 3 orders of magnitude, as a result of improved charge carrier concentrations. Hall effect reveal a charge carrier mobility reaching ∼22 cm2/Vs for ZnPc-pz-I2, which represent a record value for 2D c-COFs. An improved mobility upon doping can be traced to an increase in scattering time for free charge carriers, indicating that scattering mechanisms limiting the mobility are mitigated by doping.

In the second part of my talk, I present the results concerning a Fe3(THT)2 (THT=2,3,6,7,10,11-hexathioltriphenylene) 2D MOFs [3]. The π-d conjugated samples, synthesized through interfacial method at room temperature, are obtained as a large-area, free-standing films with tunable geometry (size and thickness). The Fe3(THT)2 films are porous (specific surface area of 526±5 m2/g) and semiconducting (with a ~250 meV direct bandgap), and remarkably display band-like charge transport. This finding is directly demonstrated from the Drude-type high-frequency (terahertz) photo-conductivity response obtained in the samples; revealing free-moving, delocalized charge carriers displaying ~220 cm2/Vs mobilities at room temperature; a record charge carrier mobility for MOFs. The temperature dependence of the mobility reveals that the main scattering mechanism limiting the mobility and hence band-like charge transport in this material is related to impurity scattering, so that material improvements may further increase the mobility.

The demonstration of band-like charge transport and record-high mobilities in semiconducting 2D COFs and MOFs reveal the potential of (porous) electrically conductive 2DLMs to be employed as active materials in opto-electronics devices.

References:

[1] “Unveiling electronic properties in metal-phthalocyanine-based pyrazine-linked conjugated two-dimensional colvalent organic frameworks” Mingchao Wang, Marco Ballabio, Mao Wang, Hung-Hsuan Lin, Bishnu Prasad Biswal, Xiaocang Han, Silvia Paasch, Eike Brunner, Pan Liu, Mingwei Chen, Mischa Bonn, Thomas Heine, Shengqiang Zhou, Enrique Canovas*, Renhao Dong*, Xinliang Feng*, JACS 141, 16810-16816, 2019.

[2] “High-Mobility Semiconducting Two-Dimensional Conjugated Covalent Organic Frameworks with p-Type Doping” Mingchao Wang, Mao Wang, Hung-Hsuan Lin, Marco Ballabio, Haixia Zhong, Mischa Bonn, Shengqiang Zhou, Thomas Heine, Enrique Cánovas*, Renhao Dong*, Xinliang Feng*, JACS 142, 21622-21627, 2020.

[3] “High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework” Renhao Dong#, Peng Han#, Himani Arora, Marco Ballabio, Melike Karakus, Zhe Zhang, Chandra Shekhar, Peter Adler, Petko St. Petkov, Artur Erbe, Stefan C. B. Mannsfeld, Claudia Felser, Thomas Heine, Mischa Bonn, Xinliang Feng* & Enrique Cánovas* Nature Materials 17, 1027-1032 (2018)