A Simple Molecular Design for Tunable Two-Dimensional Imine Covalent Organic Frameworks for Optoelectronic Applications

Two-dimensional covalent organic frameworks (2D-COFs) belong to a new class of molecular materials that have attracted huge attention in recent years due to their analogous nature to graphene. In this work, we present a systematic study of the electronic structure, carrier mobility and work function of imine based 2D-COFs. We identify these 2D-COFs as a new class of semiconducting materials with tunable electronic/optoelectronic properties and significant mobility. The results show that by rationally doping 2D-COFs at the molecular level, it is possible to control their structural and optoelectronic responses. Cohesive energy calculations revealed that all the studied 2D-COFs are thermodynamically stable. Also, the calculated binding energy of 2D-COFs on HOPG was found to be less than 1 eV, which indicates that the COFs do not interact strongly with HOPG, and it will not affect their electronic properties. Additionally, we have synthesized a 2,4,6-pyrimidinetriamine based 2D-COF and experimentally measured its band gap using scanning tunnelling spectroscopy. The experimentally measured band gap is found to be in good agreement with theoretical results.