Control of Surface and Edge Oxidation on Phosphorene

Kuntz, Kaci L.; Wells, Rebekah A.; Hu, Jun; Yang, Teng; Dong, Baojuan; Guo, H.; Woomer, Adam H.; Druffel, Daniel L.; Alabanza, Anginelle M.; Tománek, David; Warren, Scott C.

doi:10.1021/acsami.6b16111

Cited by 153 publications

(211 citation statements)

References 77 publications

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“…Indeed, the presence of electronegative groups such as oxygen or hydroxide on the surface of bP withdraws charge leading to more tightly bound phosphorus electrons. As a result, PxOy species experience a higher binding energy for P 2p core electrons in comparison to un-oxidized material [36]. Thus, we determine an average thickness of phosphorus oxide of (13.9 ± 0.4) Å for pristine bP and of (6.2 ± 0.4) Å for Ni/2D bP after aging.…”

Section: X-ray Photoemission and Absorption Spectroscopy Studymentioning

confidence: 98%

Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles

et al. 2020

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Since its discovery, the environmental instability of exfoliated black phosphorus (2D bP) has emerged as a challenge that hampers its wide application in chemistry, physics, and materials science. Many studies have been carried out to overcome this drawback. Here we show a relevant enhancement of ambient stability in few-layer bP decorated with nickel nanoparticles as compared to pristine bP. In detail, the behavior of the Ni-functionalized material exposed to ambient conditions in the dark is accurately studied by TEM (Transmission Electron Microscopy), Raman Spectroscopy, and high resolution X-ray Photoemission and Absorption Spectroscopy. These techniques provide a morphological and quantitative insight of the oxidation process taking place at the surface of the bP flakes. In the presence of Ni NPs, the decay time of 2D bP to phosphorus oxides is more than three time slower compared to pristine bP, demonstrating an improved structural stability within twenty months of observation.

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Section: X-ray Photoemission and Absorption Spectroscopy Studymentioning

confidence: 98%

Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles

et al. 2020

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“…Other studies have demonstrated the stability of this oxide in both a stoichiometric and nonstoichiometric configuration, with a direct gap tuning by means of crystal strain and electric fields . These theoretical studies will contribute to achieving technological applications for phosphorene oxide, among which there are gas sensing and gas catalysis, as well as possible humidity detection . The oxidation of the BP could favor the use of this material as a gas sensor or in other opto‐electronic applications.…”

Section: Introductionmentioning

confidence: 88%

“…Due in part to monolayer's unique electronic properties, in particular, its high surface/volume ratio. It is also possible to manipulate the electronic properties in these materials using functionalization, whether it is by doping, the presence of structural defects, or by creating heterostructures that combine monolayers of different chemical compositions …”

Section: Introductionmentioning

confidence: 99%

Opto‐electronic properties of blue phosphorene oxide with and without oxygen vacancies

Zuluaga-Hernandez

Flórez

Dorkis

et al. 2019

Int J of Quantum Chemistry

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Blue phosphorene is an attractive nanomaterial that exhibits some remarkable optoelectronic properties. Various studies have verified its ability to adsorb gaseous compounds and, in particular, to dissociate O 2 , forming covalent bonds between phosphorus and oxygen atoms. These covalent bonds could be the reason behind the oxidation reaction that affects the blue phosphorene in normal room conditions. Theoretically, it has been demonstrated that the blue phosphorene oxide (BPO) is just as stable as the blue phosphorene. Given that metallic oxides are widely used as catalyzers and gas sensors, this opens the possibility of the BPO being presented as a gas sensor as well. For all the above, in this work the optoelectronic properties of BPO were studied, along with the generation of the oxygen vacancies. The investigation was performed within the density functional theory (DFT). In the study of the oxygen vacancy, the formation energy was calculated, and the results are similar to the formation energies of oxygen vacancies in other known oxides. It was found that the BPO with a single vacancy has a favorable energetic stability. The characterization of the vacancy is achieved using the electronic structure and the optical response. Additionally, the analysis of the adsorption of a hydrogen atom on the BPO, and the subsequent formation of hydroxide is presented.Blue Phosphorene Oxide, DFT, oxygen vacancies, phosphorene 1 | INTRODUCTION Two-dimensional materials have become popular in the past decade as possible candidates for the development of applications in optoelectronics and gas-sensor manufacturing. Due in part to monolayer's unique electronic properties, in particular, its high surface/volume ratio. It is also possible to manipulate the electronic properties in these materials using functionalization, whether it is by doping, the presence of structural defects, or by creating heterostructures that combine monolayers of different chemical compositions. [1][2][3][4][5][6][7][8][9][10][11][12] Phosphorene is one of those materials that show attractive electronic features. Several theoretical studies have been conducted to evaluate the possible applications of its monolayer form as well as the realization of multilayered structures based on it. For instance, recent studies on this material have shown that it is, in fact, a nanosystem with an electronic bandgap, which can be controlled by modifying the number of layers. [13] In this sense, phosphorene becomes a promising nanosystem due, in the first place, to its physical-chemical properties and, secondly, for the challenge that poses maintaining its structural stability at room conditions, since it has revealed itself as a highly reactive material. Thus, interactions with some gases might induce significant changes in its electronic structure.

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“…[40,43,49] Moreover, the edges and steps undergo rapid degradation in few-layered samples, where the role of vacancy defects is understandably negligible. [44,46] It is also observed that the oxidation rate increases with the reduction in the number of layers, [41,45] which indicates a stronger interaction of oxygen at the surface. Formation energies E f of the SV(5|9) and SV(55|66) defects at the apical layer with varied layer thickness.…”

Section: Introductionmentioning

confidence: 95%

“…Although the exact mechanism continues to be investigated, it is understood that the strong chemical bonding between lone pair electrons of phosphorus and π * electrons of oxygen initiate the chemical degradation. [40][41][42][43][44][45][46][47][48][49] Further, degradation is accelerated as the hydrophilicity of phosphorene increases with oxidation. [40,43,49] Moreover, the edges and steps undergo rapid degradation in few-layered samples, where the role of vacancy defects is understandably negligible.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic insights in phosphorene degradation

Babar

Kabir

2019

Phys. Rev. Materials

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The structural and chemical degradations of phosphorene severely limit its practical applications despite the enormous promise. In this regard, we investigate a plethora of microscopic kinetic mechanisms and develop a degradation phase diagram within the first-principles calculations. At 400 K, the degradation and the competing self-annealing proceeds through the merger and annihilation of vacancies, respectively, which are triggered via itinerant vacancy and adatom. A further increase in temperature beyond 650 K, the structural degradation results through the emission of the undercoordinated atoms from the defect and the concurrent pair-wise sublimation. The role of inter-layer vacancy diffusion is discarded in the context of structural degradation. The chemical degradation is routed through the dissociation of oxygen molecule that is either activated at the room-temperature on the pristine surface or spontaneous at the single-vacancy site. The present results are in agreement with the few available experimental conjectures and will motivate further efforts.arXiv:1904.08822v1 [cond-mat.mes-hall]

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Control of Surface and Edge Oxidation on Phosphorene

Cited by 153 publications

References 77 publications

Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles

Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles

Opto‐electronic properties of blue phosphorene oxide with and without oxygen vacancies

Mechanistic insights in phosphorene degradation

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