Local Electronic Structure of Molecular Heterojunctions in a Single‐Layer 2D Covalent Organic Framework
[1];
- Department of Physics University of California – Berkeley Berkeley CA 94720 USA
- Laboratory for Computational and Theoretical Chemistry of Advanced Materials Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955‐6900 Kingdom of Saudi Arabia
- Department of Chemistry Kavli Energy NanoScience Institute and Berkeley Global Science Institute University of California – Berkeley Berkeley CA 94720 USA, Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
- School of Physical Sciences &, CAS Center for Excellence in Topological Quantum Computation University of Chinese Academy of Sciences Beijing 100190 P. R. China
- Laboratory for Computational and Theoretical Chemistry of Advanced Materials Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955‐6900 Kingdom of Saudi Arabia, School of Chemistry and Biochemistry &, Center for Organic Photonics and Electronics Georgia Institute of Technology 901 Atlantic Drive NW Atlanta GA 30332‐0400 USA
- Department of Physics University of California – Berkeley Berkeley CA 94720 USA, Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, Kavli Energy NanoScience Institute University of California Berkeley Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Abstract The synthesis of a single‐layer covalent organic framework (COF) with spatially modulated internal potentials provides new opportunities for manipulating the electronic structure of molecularly defined materials. Here, the fabrication and electronic characterization of COF‐420: a single‐layer porphyrin‐based square‐lattice COF containing a periodic array of oriented, type II electronic heterojunctions is reported. In contrast to previous donor–acceptor COFs, COF‐420 is constructed from building blocks that yield identical cores upon reticulation, but that are bridged by electrically asymmetric linkers supporting oriented electronic dipoles. Scanning tunneling spectroscopy reveals staggered gap (type II) band alignment between adjacent molecular cores in COF‐420, in agreement with first‐principles calculations. Hirshfeld charge analysis indicates that dipole fields from oriented imine linkages within COF‐420 are the main cause of the staggered electronic structure in this square grid of atomically–precise heterojunctions.
- Sponsoring Organization:
- USDOE
- Grant/Contract Number:
- DEAC02‐05CH11231
- OSTI ID:
- 1483708
- Journal Information:
- Advanced Materials, Journal Name: Advanced Materials Vol. 31 Journal Issue: 3; ISSN 0935-9648
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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