Defected and Functionalized Germanene-based Nanosensors under Sulfur Comprising Gas Exposure

Abstract

Efficient sensing of sulfur containing toxic gases like H₂S and SO₂ is of the utmost importance due to the adverse effects of these noxious gases. Absence of an efficient 2D-based nanosensor capable of anchoring H₂S and SO₂ with feasible binding and an apparent variation in electronic properties upon the exposure of gas molecules has motivated us to explore the promise of a germanene nanosheet (Ge-NS) for this purpose. In the present study, we have performed a comprehensive computational investigation by means of DFT-based first-principles calculations to envisage the structural, electronic, and gas sensing properties of pristine, defected, and metal substituted Ge-NSs. Our initial screening has revealed that although interaction of SO₂ with pristine Ge-NSs is within the desirable range, H₂S binding however falls below the required values to guarantee an effective sensing. To improve the binding characteristics, we have considered the interactions between H₂S and SO₂ with defected and metal substituted Ge-NS. The systematic removals of Ge atoms from a reasonably large super cell lead to monovacancy, divacancies, and trivacancies in Ge-NS. Similarly, different transition metals like As, Co, Cu, Fe, Ga, Ge, Ni, and Zn have been substituted into the monolayer to realize substituted Ge-NS. Our van der Waals corrected DFT calculations have concluded that the vacancy and substitution defects not only improve the binding characteristics but also enhance the sensing propensity of both H₂S and SO₂. The total and projected density of states show significant variations in electronic properties of pristine and defected Ge-NSs before and after the exposure to the gases, which are essential in constituting a signal to be detected by the external circuit of the sensor. We strongly believe that our present work would not only advance the knowledge towards the application of Ge-NS-based sensing but also provide motivation for the synthesis of such efficient nanosensor for H₂S and SO₂ based on Ge monolayer.