Electronic Properties of Two-Dimensional Kagome Lattice Based on Transition Metal Phthalocyanine Heterojunctions

Transition metal phthalocyanine molecules serve as building blocks for two-dimensional (2D) metal-organic frameworks with potential applications in optics, electronics, and spintronics. Previous theoretical studies predicted that a two-dimensional transition metal phthalocyanine framework with kagome lattice (kag-TMPc) has stable magnetically ordered properties, which are promising for spintronics and optoelectronics. However, there is a lack of studies on their heterojunctions, which can effectively tune the properties through interlayer coupling despite its weak nature. Here we use density functional theory (DFT) to calculate the electronic properties of eight representative 2D kag-TMPc vertical heterojunctions with two different stackings (AA and AB) and interlayer distances. We found that most of the kag-MnPc-based heterojunctions can maintain the electronic properties of monolayer materials with low bandgap. kag-MnPc/ZnPc are ferromagnetic semiconductors with magnetic exchange energy above 40 meV, regardless of stacking sequences; the electronic properties of kag-MnPc/MnPc heterojunctions change from magnetic half-metal to magnetic semiconductor during the transition from AA stacking to AB stacking. Interestingly, the AB stacked kag-CuPc/CoPc heterojunction is a ferromagnetic semiconductor, and the spin-polarized energy band arrangement changes with the layer spacing: when the layer spacing is at the equilibrium distance, the spin-up and spin-down energy bands are aligned as type II; when the layer spacing increases by 0.2 Å, the spin-up energy bands are aligned as type I, while the spin-down energy bands are aligned as type II energy bands. This distance-dependent spin properties can realize magnetic optoelectronic "switching" and has potential applications in new magnetic field modulated lectromagnetic and optoelectronic devices.