Tuning the structural, electronic and dynamical properties of Janus M4X3Y3 (M = Pd, Ni and Co; X,Y = S, Se and Te) monolayers: a DFT study

Based on density functional theory, the structural, electronic and vibrational properties of two-dimensional transition metal chalcogenides M2X3 and their Janus type M4X3Y3, where M = Pd, Co and Ni and X = Se, S and Te, are investigated. Motivated by the successful synthesis of a 2D Pd2Se3 monolayer and the proof of the dynamical stability of Ni2Se3 and Co2Se3 monolayers, in terms of the phonon band dispersions, we have systemically studied the fundamental physical properties of Janus transition metal chalcogenides, such as their structural, phonon and thermodynamic stability and their electronic and mechanical properties. Our results show that Janus structures of M4X3Y3 are energetically favorable and dynamically stable. The ab initio molecular dynamic simulations (AIMD) results clearly prove that they kept their thermal stability at room temperature. We have demonstrated their structural, electronic and vibrational properties and Raman spectra. The electronic band dispersions show that monolayer Co2Se3 shows half-metal properties with a moderate band gap (1.01 eV), Pd2Se3 has a 1.42 eV direct band gap, while Ni2Se3 has a 1.38 eV indirect band gap. Pd4Se3S3, Pd4Se3Te3 and Pd4S3Te3 are indirect band gap semiconductors with band gaps of 1.22 eV, 1.05 eV and 0.61 eV, respectively. Ni4Se3S3, Ni4Se3Te3 and Ni4S3Te3 are indirect band gap semiconductors with band gaps of 1.61 eV, 0.77 eV and 0.49 eV, respectively. While pristine Co2Se3 is shown to have half-metallicity (HM), the HM behaviour of the Janus Co4Se3Te3 and Co4S3Te3 monolayers disappear and Co4Se3S3 remains a HM with a moderate band gap of 0.85 eV. In addition, the Raman spectra of these Janus materials are shown to exhibit totally distinctive features as compared to those of the pristine materials. This work reveals the important material properties of Janus type M4X3Y3 monolayers, where M = Pd, Co and Ni and X = Se, S and Te, which could have wide applications in new functional devices. KLUBAP [201] Computational resources were provided by the TUBITAK ULAKBIM High Performance and Grid Computing Center (TR-Grid e-Infrastructure). B. Akgenc acknowledges financial support from the KLUBAP under Project Number 201.