Charge Transfer and Functionalization of Monolayer InSe by Physisorption of Small Molecules for Gas Sensing

Cai, Yongqing; Zhang, Gang; Zhang, Yong‐Wei

doi:10.1021/acs.jpcc.7b02286

Cited by 89 publications

(105 citation statements)

References 83 publications

(186 reference statements)

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“…As shown above, the H2O molecule acts as a donor to bismuthene, which is similar to the role of H2O in the case of its adsorbtion on phosphorene, while for arsenene, InSe, and antimonene the H2O molecule is an acceptor. 78,79,81 Based on the calculated adsorbtion energy and the charge transfer analyses, the performance of 2D pnictogens and InSe is highly sensitive to the environmental O2 molecule rather than the H2O molecule.…”

Section: Resultsmentioning

confidence: 99%

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Environmental stability of bismuthene: oxidation mechanism and structural stability of 2D pnictogens

et al. 2019

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Recently a new group of two-dimensional (2D) materials, originating from the group V elements (pnictogens), has gained global attention owing to their outstanding properties. Due to a high surface-volume ratio and extraordinary chemical activity, 2D pnictogens such as phosphorene and antimonene are highly sensitive to exposure to the environment. Hence, upon the exposure to oxygen and water molecules, they may easily oxidize, which leads to the degradation of their structure. In this work, we perform a first-principles investigation on the effects of the environmental oxygen and water molecules on the structural stability of newly emerged group V 2D material bismuthene. It is proposed that the oxidation process of bismuthene and other 2D pnictogens at ambient сonditions сan involve three general steps: adsorption of oxygen moleсules; dissoсiation of oxygen moleсules; interaсtion of water moleсules with the oxygen speсies anсhored at the surface to form acids. Importantly, recent experiments reported on high stability of bismuthene even at high temperatures. Here we show that the underlying reason for such structural stability of bismuthene may have similar roots as the stability of antimonene which originates from an acceptor role of water molecules on that material while in the case of materials with the lower stability, like phosphorene and InSe, water molecules act as donors. The present work uncovers the oxidation mechanisms and suggests the ways for maintaining the stability of bismuthene and its 2D pnictogens counterparts, which may be important for their fabrication, storage, and applications.

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Section: Resultsmentioning

confidence: 99%

“…Such structural changes upon the O2 molecule dissociation on the bismuthene surface is similar to that of its counterparts: phosphorene, arsenene, antimonene and InSe. 71,[78][79][80][81][82][83]…”

Section: Oxidation Kinetics and Mechanisms Of The Structural Degradatmentioning

confidence: 99%

Environmental stability of bismuthene: oxidation mechanism and structural stability of 2D pnictogens

et al. 2019

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“…The local density of states (LDOS) plot (Figure 1d) shows that the highest occupied molecular orbital (HOMO) 5σ and the lowest unoccupied molecular orbital (LUMO) 2π * of the CO molecule adsorbed on antimonene are located at −4.30 and 2.10 eV (relative to the Fermi level), respectively.It should be noted that the HOMO level is a non-resonant state located below the valence band of antimonene, while the LUMO level is located within the conduction band. The 2π * peak is significantly broadened compared with the 5σ level, which is opposite to the case of CO above InSe 54. This alignment of CO LUMO states within the conduction band of antimonene suggests that the photo-excited electrons of antimonene may partially transfer to the CO LUMO state, which can trigger a different electron-hole recombination rate and prolong the lifetime of holes in the antimonene sheet upon exposure to the CO gas.…”

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confidence: 77%

A first-principles study on the adsorption of small molecules on antimonene: oxidation tendency and stability

et al. 2018

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Antimonene, a new group-VA 2D semiconducting material beyond phosphorene, was recently synthesized through various approaches and was shown to exhibit a good structural integrity in ambient conditions and various interesting properties. In this work, we perform systematical first-principles investigations on the interactions of antimonene with the small molecules CO, NO, NO2, H2O, O2, NH3 and H2. It is found that NO, NO2, H2O, O2, and NH3 serve as charge acceptors, while CO shows a negligible charge transfer. H2 acts as a charge donor to antimonene with the amount of charge transfer being ten times that of H2 on phosphorene. The interaction of the O2 molecule with antimonene is much stronger than that with phosphorene. Surprisingly, the kinetic barrier for the splitting of the O2 molecule on antimonene is low (~0.40 eV), suggesting that pristine antimonene may undergo oxidation in ambient conditions, especially at elevated temperatures. Fortunately, the acceptor role of H2O on antimonene, opposite to a donor role in phosphorene, helps to suppress further structural degradation of the oxidized antimonene by preventing the proton transfer between water molecules and oxygen species to form acids. By comparing antimonene with phosphorene and InSe, we suspect that the acceptor role of water may be a necessary condition for a good environmental stability of such 2D layers to avoid structural decomposition. While the surface oxidation layer may serve as an effective passivation layer from further degradation of the underlying layers, our findings show that antimonene layers still need to be separated or properly protected by other noncovalent functionalization from oxygen or other environmental molecules. The present work reveals interesting insights into the environmental effects of physisorbed small molecules on the oxidation tendency and stability of antimonene, which may be important for its growth, storage and applications.

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“…In addition to the InSe-graphene/BN bilayer system, we also considered the periodic InSegraphene/BN superlattice with the sequential stacking of InSe and graphene/BN along the normal direction. As there exist the lone-pair electronic states in the top Se atoms, 20 we are interested in modulating the electronic structure of the hybrids, in particular, to see any indirect-direct transition of InSe, by changing the van der Waals gap. The modified interlayer distance di should significantly affect the hybridization of the Se states and the graphene and BN states.…”

Section: Computational Detailsmentioning

confidence: 99%

Effects of graphene/BN encapsulation, surface functionalization and molecular adsorption on the electronic properties of layered InSe: a first-principles study

Kistanov

Cai

Zhou

et al. 2018

Phys. Chem. Chem. Phys.

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By using first-principles calculations, we investigated the effects of graphene/boron nitride (BN) encapsulation, and surface functionalization by metallic elements (K, Al, Mg and typical transition metals) and molecules (tetracyanoquinodimethane (TCNQ) and tetracyanoethylene (TCNE)) on the electronic properties of layered indium selenide (InSe). It was found that an opposite trend of charge transfer is possible for graphene (donor) and BN (acceptor), which is dramatically different from phosphorene where both graphene and BN play the same role (donor). For an InSe/BN heterostructure, a change of the interlayer distance due to out-of-plane compression can effectively modulate the band gap. Strong acceptor abilities to InSe were found for the TCNE and TCNQ molecules. For K, Al and Mg-doped monolayer InSe, charge transfer from the K and Al atoms to the InSe surface was observed, causing an n-type conduction of InSe, while p-type conduction of InSe was observed in the case of Mg-doping. The atomically thin structure of InSe enables the possible observation and utilization of the dopant-induced vertical electric field across the interface. A proper adoption of the n- or p-type dopants allows for the modulation of the work function, the Fermi level pinning, the band bending, and the photo-adsorbing efficiency near the InSe surface/interface. Investigation of the adsorption of transition metal atoms on InSe showed that Ti-, V-, Cr-, Mn-, and Co-adsorbed InSe are spin-polarized, while Ni-, Cu-, Pd-, Ag- and Au-adsorbed InSe are non-spin-polarized. Our results shed light on the possible ways to protect InSe structures and modulate their electronic properties for nanoelectronics and electrochemical device applications.

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Charge Transfer and Functionalization of Monolayer InSe by Physisorption of Small Molecules for Gas Sensing

Cited by 89 publications

References 83 publications

Environmental stability of bismuthene: oxidation mechanism and structural stability of 2D pnictogens

Environmental stability of bismuthene: oxidation mechanism and structural stability of 2D pnictogens

A first-principles study on the adsorption of small molecules on antimonene: oxidation tendency and stability

Effects of graphene/BN encapsulation, surface functionalization and molecular adsorption on the electronic properties of layered InSe: a first-principles study

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