Robust intrinsic ferromagnetism and half semiconductivity in stable two-dimensional single-layer chromium trihalides

Two-dimensional (2D) intrinsic ferromagnetic (FM) semiconductors are crucial to develop low-dimensional spintronic devices. Using density functional theory, we show that single-layer chromium trihalides (SLCTs) (CrX3, X = F, Cl, Br and I) constitute a series of stable 2D intrinsic FM semiconductors. A free-standing SLCT can be easily exfoliated from the bulk crystal, due to a low cleavage energy and a high in-plane stiffness. Electronic structure calculations using the HSE06 functional indicate that both bulk and single-layer CrX3 are half semiconductors with indirect gaps and their valence and conduction bands are fully spin-polarized in the same spin direction. The energy gaps and absorption edges of CrBr3 and CrI3 are found to be in the visible frequency range, which implies possible opto-electronic applications. Furthermore, SLCTs are found to possess a large magnetic moment of 3 μB per formula unit and a sizable magnetic anisotropy energy. The magnetic exchange constants of SLCTs are then extracted using the Heisenberg spin Hamiltonian and the microscopic origins of the various exchange interactions are analyzed. A competition between a near 90° FM superexchange and a direct antiferromagnetic (AFM) exchange results in a FM nearest-neighbour exchange interaction. The next and third nearest-neighbour exchange interactions are found to be FM and AFM, respectively, and this can be understood by the angle-dependent extended Cr–X–X–Cr superexchange interaction. Moreover, the Curie temperatures of SLCTs are also predicted using Monte Carlo simulations and the values can be further increased by applying a biaxial tensile strain. The unique combination of robust intrinsic ferromagnetism, half semiconductivity and large magnetic anisotropy energies renders the SLCTs as promising candidates for next-generation semiconductor spintronic applications.