Scandium doping of black phosphorene for enhanced sensitivity to hydrogen sulfide: Periodic DFT calculations
Graphical abstract
Introduction
Environmental protection, health, and safety subjects have resulted in gas sensors to become essential elements of modern society. The use of chemosensors is widespread in many industrial production and public security fields [1,2]. Two-dimensional nanostructured devices exhibit intriguing features for the detection of various toxic molecules [[3], [4], [5], [6], [7], [8]]. Specifically, phosphorene monolayer has attracted a number of researchers to investigate the less understood physical and chemical properties in detail [[9], [10], [11]]. The behavior of BP toward different adsorbate species or analytes can be further modulated using functionalization and doping, the detailed account of which is summarized in a recent work by the authors of the present study [12].
Hydrogen sulfide is considered to be one of the main environmental pollutants and a flammable gas which occurs in anthropogenic and natural environments; H2S can be dangerous at very low concentration as well. Therefore, substantial research studies have been conducted in order to find novel gas sensors for the detection and monitoring of H2S in many manufacturing industries [[13], [14], [15]]. CuO-single wall carbon nanotube structures were synthesized to detect the H2S concentration up to 100 ppb at room temperature [16]. The performance of the fabricated nanostructures for monitoring of H2S molecules was evaluated in terms of a long life-time (30 days) and repeatability. Ni-doped InN monolayer has shown great performance for hydrogen sulfide adsorption with the adsorption energy value of −1.57 eV [17]. In another work, Mn doping resulted in the enhancement of charge transfer to 0.171 e and the adsorption energy to 4.3228 eV between graphene and H2S [18].
Silicene nanoribbons (SiNRs) form another class of nanosensors with an excellent capability in terms of hydrogen sulfide adsorption [19]. Faye et al. [20] demonstrated that a high amount of energy is liberated during the hydrogen sulfide dissociation on S-doped graphene and the subsequent formation of chemically bonded HSSH. According to the aforementioned results, hydrogen sulfide capturing capability could be improved by the S dopant in the single-vacancy defects. The black phosphorene current-voltage characteristics experience a considerable change when hydrogen sulfide molecules are present in the system [21]. Single ultrathin WO3 nanowire, conductive polypyrrole, and Pt-decorated phosphorene have also shown the great capability for hydrogen sulfide detection [[22], [23], [24]]. The pristine phosphorene surface was found to be more sensitive to hydrogen sulfide and sulfate molecules than other similar nanodevices which were modified by doping of iron, titanium, manganese, or silicon [25].
Scandium and its compounds are also used in the semiconductor industry as the dopant or the primary substrate. Sc-doped semiconductor materials are the simplest rare-earth metal- and transition metal-doped devices. For instance, Liu et al. have shown through the adaptive natural density partitioning analysis of the ScSin structures that a fully encapsulated anionic cluster with n = 16 is a magic configuration with good thermodynamic and chemical stability [26]. Nobuhito et al. showed that the addition of scandium oxide (Sc2O3) notably enhanced the sensing performance of nickel-copper oxide for the NO2 molecule [27]. Previous reports have shown that the inclusion of Sc in the aluminum nitride to form the ScAlN alloys can strongly affect the piezoelectric coefficients until a phase transition to a non-polar rocksalt-type structure [[28], [29], [30]]. Chen and coworkers have also shown that the Sc doping into the so-called LSCM perovskite material could remarkably improve the electrode polarization and offer higher oxide-ion conductivity for the direct steam electrolysis while reducing the electronic conductivity [31]. An investigation by Sha and coworkers has recently demonstrated the giant sensitivity of lanthanide-doped Sc2O3 as a rare-earth oxide low-temperature optical sensor [32].
Wang et al. have identified, through first-principles calculations, a new class of 2D scandium carbide structures with an exceptionally stable Sc3C10 primitive cell, which contained two pentagonal carbon rings encompassed by one scandium octagon. The predicted nanosheets could serve as a precursor for the corresponding Volleyballene Sc20C60 and metallic (ScC) nanotubes [33]. Another DFT study by Wang et al. has demonstrated that the Sc decoration of B-doped porous graphene (PG) could provide the capability for the adsorption of five H2 molecules around the adatom with the average adsorption energy of −0.52 eV [34]. Manjunatha and coworkers investigated the influence of Sc content on the humidity sensing performance of the resulting cobalt chromate [Co(1–x)ScxCr2O4] nanoparticles [35]. According to Arıkan and coworkers, the calculated elastic, electronic, and phonon properties corroborated the mechanical stability and ductility of the ScX3 type of metal structures (X = Ir, Pd, Pt, and Rh) [36]. In another study by Cai et al. the adsorption energy of an Sc adatom on phosphorene was increased and decreased by the compressive and tensile strains, respectively, which in turn altered the magnetic moments and the magnetic coupling states of the adatom. These changes can be exploited to provide great potential in the spintronic field [37]. Zhiyuan et al. have also proposed that transition metals (e.g., scandium) and lanthanides can be used as prospective decoration elements for hydrogen-storage on phosphorene [38]. Babar and Kabir discussed that the three valence electrons of the Sc dopant completely saturates the three dangling bonds at the phosphorene vacancy, thus leading to no local moment [39]. For a decorated layer, Zhu et al. showed that the Sc adatom creates a spontaneous spin-polarization and a total magnetic moment of 1.00 μB [40]. Rahimi and Zabaradsti have shown theoretically that the optical properties of a B12N12 nanocage can be improved by Sc-substitution for the detection of H2S molecule [15]. Beheshtian et al. have also demonstrated that the Sc-doping can enhance the sensing properties of the boron nitride nanotube (BNNT) toward phosgene [41].
Herein, inspired by the background given above, it was presented that substitutional doping can remarkably improve the sensitivity of the BP monolayer toward the H2S molecule. Although some papers have addressed the effect of Sc decoration for some phosphorene systems, the influence of Sc doping to provide an integrated single-layer hydrogen sulfide sensor has not been investigated so far. For this purpose, we test for the first time the electronic performance of scandium doping of black phosphorene in terms of higher sensitivity for the hydrogen sulfide molecule. Possible improvement in this regard should be accompanied by appropriate reusability for practical application. Therefore, the recovery time was also explored. Finally, the obtained results can open new avenues for the systematic design of gas sensors, particularly hydrogen sulfide.
Section snippets
Computational methods
Periodic molecular simulations were implemented within the framework of CP2K [42] and NWChem 6.5 [43]. The frontier molecular orbital (FMO) computations and density of states (DOS) were afforded by Multiwfn 3.3.8 [44]. The electronic band structures were obtained by means of Burai 1.3 [45] from Quantum-Espresso 6.6 [46]. Finally, the Mercury 3.6 [47] and Avogadro 1.2.0 [48] packages were applied to visualize the outputs of the calculations. For the periodic optimizations, we employed the
Results and discussion
As pointed out previously, the simulation of black phosphorene sensors, including the pristine (BP) monolayer and the scandium-doped analog, which was labeled as SP for short, was carried out in a periodic system. The modified sensor was computationally constructed using the inclusion of the scandium heteroatom in the pristine phosphorene slab. The simulation of the adsorption configurations with hydrogen sulfide molecule was performed after the two black phosphorene sensors were modeled. The
Conclusion
The current study investigates the adsorptive and sensing properties of a modified phosphorene sensor, through scandium doping, toward hydrogen sulfide using periodic DFT calculations. Slightly different configurations were recognized for the BP and SP sensors. More strictly, the most stable geometry for the H2S molecule over the Sc-doped sensor preferred a unique configuration such that the S atom was placed on top of the Sc center and the H atoms adopted asymmetrical bridge-type placement.
CRediT authorship contribution statement
Azam Marjani: Formal analysis, Writing - original draft, Writing - review & editing, Resources. Mohammad Ghashghaee: Conceptualization, Formal analysis, Project administration, Validation, Visualization, Writing - original draft, Writing - review & editing. Mehdi Ghambarian: Conceptualization, Data curation, Methodology, Software, Formal analysis, Resources. Mahdi Ghadiri: Formal analysis, Writing - original draft, Writing - review & editing, Resources.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
Technical assistance from Ms. Mahboobeh Balar is gratefully acknowledged.
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2022, Physica E: Low-Dimensional Systems and NanostructuresCitation Excerpt :The results proved that gas adsorption and TM doping induced changes in magnetism and electrical conductivity and that the TM-doped phosphorene was a potential candidate to develop novel two-dimensional phosphorene -based gas sensors [24]. Previous reports have indicated that introducing defects and TM doping can increase the sensitivity of phosphorene toward some gas molecules [25–31]. As we all known that CH4 is the main ingredient of natural gas and has certain flammability.