Interlayer Bond Formation in Black Phosphorus at High Pressure

Scelta, Demetrio; Baldassarre, Adhara; Serrano‐Ruiz, Manuel; Dziubek, Kamil; Cairns, Andrew B.; Peruzzini, Maurizio; Bini, Roberto; Ceppatelli, Matteo

doi:10.1002/anie.201708368

Cited by 39 publications

(58 citation statements)

References 52 publications

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“…However, it does not exist naturally. BP has three crystalline structures, namely orthorhombic, rhombohedral, and simple cubic phases . We here focus on orthorhombic BP due to its unique semiconducting properties and relatively accessible synthetic conditions.…”

Section: Cvt Based Synthesis Of Black Phosphorusmentioning

confidence: 99%

Chemical Vapor Transport Reactions for Synthesizing Layered Materials and Their 2D Counterparts

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et al. 2019

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semimetals (Si and Ge) to transition metal dichalcogenides (TMDs), which can be tuned from semiconductors to superconductors, have been intensively investigated. [8] Despite the recent advances in 2D materials, it is still challenging to obtain 2D materials with desired layers and size in facile and controllable manners.Indeed, continuous research has been carried out on the synthesis of 2D materials. [9] Generally, two synthetic strategies, known as top-down and bottom-up, are applied to obtain 2D materials. In the common top-down strategy, 2D materials are exfoliated from their bulk counterparts. Differently, using the bottom-up strategy, 2D materials with a few thin layers, even an atomically thin layer, can be directly synthesized from small building blocks such as molecules and atoms. [10] In these synthetic strategies for 2D materials, chemical vapor transport (CVT) reaction, an old yet powerful technology, plays an important role because CVT reactions can be used for both topdown and bottom-up syntheses of 2D materials. [11] CVT reactions represent a category of reactions with one common feature: a condensed phase, typically a solid, sublimes in the presence of a gaseous reactant (the mineralizer), and then deposits elsewhere usually in the form of crystals. [12] Notably, CVT is different from chemical vapor deposition (CVD), another chemical vapor-based approach for synthesizing 2D materials. Specifically, the main difference between CVT and CVD lies in the source materials for synthesizing products, where solid reactants are typically used in CVT and gaseous precursors are usually applied in CVD. The difference induces consequent differences in reactor design, operational control, and product features, thus bringing strengths and drawbacks for each approach. Since the discovery of CVT reaction by Bunsen in 1851, comprehensive understanding of CVT reactions in both experimental exploration and theoretical modeling has been established. [13] Furthermore, thousands of CVT reactions have been applied till now, producing a great variety of pure and crystalline solids, including metals, metalloids, intermetallic phases, metal oxides, halides, chalcogen halides, chalcogenides, and pnictides. [13,14] The knowledge about CVT reactions, together with the large number of applicable reactions, can offer opportunities for the controllable synthesis of 2D materials and the exploration of new 2D materials. Unfortunately, for the preparation of 2D materials, in stark contrast to the wide application of CVD, 2D materials, namely thin layers of layered materials, are attracting much attention because of their unique electronic, optical, thermal, and catalytic properties for wide applications. To advance both the fundamental studies and further practical applications, the scalable and controlled synthesis of large-sized 2D materials is desired, while there still lacks ideal approaches. Alternatively, the chemical vapor transport reaction is an old but powerful technique, and is recently adopted for synthesizing 2D material...

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Section: Cvt Based Synthesis Of Black Phosphorusmentioning

confidence: 99%

Chemical Vapor Transport Reactions for Synthesizing Layered Materials and Their 2D Counterparts

Wang

Luo

Lü

et al. 2019

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“…According to literature the A7 to sc phase transition, reported to occur sharply, should be already completed at this pressure. Nevertheless, all the patterns clearly show the presence of the two extra peaks characteristic of the recently discovered p-sc structure, 9 indicating that its formation is related neither to the application of hydrostatic/non-hydrostatic conditions nor to the solidification of the PTM (He = 11.5 GPa, 13 H 2 = 5.4 GPa, 14 N 2 = 2.4 GPa, 15 Daphne Oil 7474 = 3.7 GPa 16 ). The presented data unambiguously demonstrate that the p-sc structure, recently observed using He as PTM, 9 is an intrinsic feature of the element.…”

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confidence: 93%

“…Recently, a synchrotron X-ray diffraction (XRD) study has shed new light on the phase diagram of P, demonstrating the presence of a two-step mechanism for the A7 to sc transition and unveiling the existence of an intermediate pseudo simple-cubic (p-sc) structure in the pressure range extending from 10.5 GPa up to at least ∼30 GPa 9 (ESI3 † ). Indeed, adopting a rhombohedral cell description ( R 3[combining macron] m ) for both A7 and sc structures, whereas above 10.5 GPa the angle α rapidly approaches the ∼60° limit value characteristic of the sc structure, at ∼30 GPa the atomic position u is still far from the 0.250 value expected in the sc structure, thus causing a metric pseudo-symmetry 9 ( Fig. 3 , upper panel and Fig.…”

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confidence: 99%

“…With increasing pressure, the reduction of the interlayer spacing further perturbs the electron lone pairs up to induce interlayer bond formation. The key role of the s–p orbital mixing in stabilizing the presence of electron lone pairs at tetrahedral P sites versus the sc octahedral coordination is further highlighted by the pressure delay of the P atoms in assuming the positions expected in the sc structure, 9 which is responsible for the lattice distortion observed in the p-sc structure.…”

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The p-sc structure in phosphorus: bringing order to the high pressure phases of group 15 elements

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“…Nevertheless, even if the room temperature phase diagram of P is known up to 340 GPa, a recent state‐of‐the‐art high pressure synchrotron X‐ray diffraction (XRD) experiment has shed new light on the low pressure range, with significant implications concerning the layered structures of P . The XRD patterns, acquired during the room temperature compression of black phosphorus using a membrane Diamond Anvil Cell (DAC) with He as pressure transmitting medium, revealed indeed two unexpected peaks in the sc structure, appearing at 10.5 GPa and persisting up to 27.6 GPa, the highest investigated pressure.…”

Section: High Pressure Behavior Of Black Phosphorus Layersmentioning

confidence: 99%

A Perspective on Recent Advances in Phosphorene Functionalization and Its Applications in Devices

et al. 2018

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Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in materials science. The physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in the preparation, functionalization, and use of phosphorene and its decorated derivatives. We discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behavior of black phosphorus, as well as its decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and the new results collected in our laboratories.

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Interlayer Bond Formation in Black Phosphorus at High Pressure

Cited by 39 publications

References 52 publications

Chemical Vapor Transport Reactions for Synthesizing Layered Materials and Their 2D Counterparts

Chemical Vapor Transport Reactions for Synthesizing Layered Materials and Their 2D Counterparts

The p-sc structure in phosphorus: bringing order to the high pressure phases of group 15 elements

A Perspective on Recent Advances in Phosphorene Functionalization and Its Applications in Devices

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