Chemically exfoliating large sheets of phosphorene via choline chloride urea viscosity-tuning

Ng, Amy; Sutto, Thomas E.; Matis, Bernard R.; Deng, Yuanyuan; Ye, P D; Stroud, Rhonda M.; Brintlinger, Todd; Bassim, Nabil

doi:10.1088/1361-6528/aa62f6

Cited by 12 publications

(10 citation statements)

References 32 publications

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“…Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) have been used to tailor the thickness of BP flakes, [ 27 ] while choline chloride urea, an ionic liquid, was used for the production of flakes with large lateral dimensions in the micrometer range. [ 28 ] Liquid exfoliation has therefore been established as a scalable production strategy of high‐quality BP nanosheets with minimal defects. [ 10b ]…”

Section: Structure Properties and Exfoliation Of Bpmentioning

confidence: 99%

“…[ 72 ] Therefore, the use of ILs which can easily be removed by rinsing has been investigated as a protection strategy. [ 44 ] ILs facilitate efficient high‐yield exfoliation of 2D materials [ 28,73 ] and provide a protective barrier to degradation. [ 73b ] Two ILs, 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl) imide and 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, were used for the liquid exfoliation of BP.…”

Section: Protection Strategiesmentioning

confidence: 99%

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Degradation of Black Phosphorus and Strategies to Enhance Its Ambient Lifetime

Druenen

2020

Adv Materials Inter

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water resulting in rapid decomposition, [12] making processing of the material challenging and resulting in detrimental effects on its optical and electronic properties. [13] The ambient degradation of BP presents a significant hurdle to realizing the full potential of BP in various applications. The successful application of BP will rely either on its exclusion from the factors that contribute to its degradation or protection methods that prevent its degradation in ambient conditions. Literature reports that have studied the degradation chemistry of BP have revealed some conflicting results regarding the effect of water, oxygen and light, indicating that BP has a complex surface chemistry. The indepth characterization of BP degradation is critical for the development of new protection strategies and progress of the material and its applications. The role of the surface oxide as a passivation layer that stabilizes BP has also created some debate between researchers. Although a stabilizing oxide has been reported in theoretical studies, [14] experimental reports question the challenges of creating a self-limiting surface oxide on BP. [15] Protection of BP can also be accomplished by capping layers, [13c,16] functionalization, [17] solvent passivation, [10b] or the incorporation of polymers. [18] Ambient degradation can be suppressed by covalent functionalization where chemical binding of molecules to the reactive lone pairs on the surface prevent decomposition. [17] Noncovalent functionalization can also be employed, which inhibits degradation by passivating BP nanoflakes through noncovalent interactions. [17b] Solvent passivation forms a protective barrier against oxidants while polymer coatings, or the formation of BP-polymer hybrids enhances its oxidation resistance while also modifying its properties. This review outlines the factors that influence the oxidation of BP from a surface chemistry perspective, including the effect of water, oxygen, and light on the degradation of BP, as well as elucidation of the oxidation mechanism through analysis of BP exposed to single oxidants and evaluation of the oxidation products. Additionally, an overview of current advances in the protection strategies for BP is presented. 2. Structure, Properties, and Exfoliation of BP BP has an orthorhombic crystal structure and consists of layers of phosphorene held together by van der Waals interactions, as depicted in Figure 1a. [19] The individual layers of phosphorene consist of phosphorus atoms covalently bound Exfoliation of black phosphorus (BP) into phosphorene has led to the discovery of its semiconducting properties and tunable bandgap, enabling its use in a range of applications including transistors, batteries, and sensors. However, BP's ambient instability poses a considerable challenge to its incorporation into functional devices. Observed changes to the surface chemistry of BP during degradation has recently provided insight into the degradation pathways. In this review, degradation mechanisms are discussed including th...

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Section: Structure Properties and Exfoliation Of Bpmentioning

confidence: 99%

Section: Protection Strategiesmentioning

confidence: 99%

Degradation of Black Phosphorus and Strategies to Enhance Its Ambient Lifetime

Druenen

2020

Adv Materials Inter

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“…13 While graphene, silicene, germanene and phosphorene have been extensively studied in recent years, 12,14 arsenene, antimonene and bismuthene have been mostly explored using theoretical calculations. [14][15][16][17][18][19][20] Especially for arsenene and its experimentally synthetic methods, there have been a limited number of reports.…”

Section: Introductionmentioning

confidence: 99%

Acetonitrile-assisted exfoliation of layered grey and black arsenic: contrasting properties

et al. 2020

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“…Alkali metals have been used to alter the properties of BP, [15] but the resulting intercalation complexes suffer from poor ambient stability, [16] while intercalation with alkyl ammonium salts can stabilize BP [17] . Tetrabutylammonium salts have been used for the formation of BP intercalation compounds under electrochemical conditions, which enhanced the efficiency of exfoliation, [18] while ammonium salts have proven to have a facilitative effect on BP exfoliation through edge intercalation, which overcomes the interlayer van der Waals forces [14b] . Herein, a scalable protection strategy is presented in which simultaneous exfoliation and functionalization are achieved through sonication of BP in a solution containing a tetrabutylammonium salt and an aryl iodide.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of Black Phosphorus by Sonication‐Assisted Simultaneous Exfoliation and Functionalization

Druenen

Collins

Davitt

et al. 2020

Chemistry A European J

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Black phosphorus (BP) has extraordinary properties, but its ambient instability remains ac riticalc hallenge. Functionalization has been employed to overcome the sensitivity of BP to ambient conditions while preserving its properties. Herein, as imultaneous exfoliation-functionalization process is reported that functionalizes BP flakes during exfoliation and thus provides increased protection, which can be attributed to minimal exposure of the flakes to ambient oxygen and water.At etrabutylammonium salt was employed for intercalation of BP,r esulting in the formation of flakes with large lateral dimensions. The addition of an aryl iodide or an aryl iodoniums alt to the exfoliation solventc reates as calable strategy for the production of functionalized few-layer BP flakes. The ambient stability of functionalized BP was prolonged to ap eriod of one week, as revealed by STEM, AFM,and X-ray photoelectron spectroscopy.

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Chemically exfoliating large sheets of phosphorene via choline chloride urea viscosity-tuning

Cited by 12 publications

References 32 publications

Degradation of Black Phosphorus and Strategies to Enhance Its Ambient Lifetime

Degradation of Black Phosphorus and Strategies to Enhance Its Ambient Lifetime

Acetonitrile-assisted exfoliation of layered grey and black arsenic: contrasting properties

Stabilization of Black Phosphorus by Sonication‐Assisted Simultaneous Exfoliation and Functionalization

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