The Extended Stability Range of Phosphorus Allotropes

Bachhuber, Frederik; Appen, Jörg von; Dronskowski, Richard; Schmidt, Peer; Nilges, Tom; Pfitzner, Arno; Weihrich, Richard

doi:10.1002/anie.201404147

Cited by 154 publications

(186 citation statements)

References 52 publications

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“…Distinct configurations were generated by employing the conformational space annealing algorithm for global optimization. We find that black phosphorus is the most stable allotrope at zero temperature, as reported previously [26]. Among various metastable configurations [27], we obtained a novel allotrope in the space group C2/m, which contains 6 atoms in the primitive cell.…”

supporting

confidence: 82%

Prediction of Green Phosphorus with Tunable Direct Band Gap and High Mobility

Han

Kim

Lee

et al. 2017

J. Phys. Chem. Lett.

108

102

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Based on ab initio evolutionary crystal structure search computation, we report a new phase of phosphorus called green phosphorus (λ-P), which exhibits the direct band gaps ranging from 0.7 to 2.4 eV and the strong anisotropy in optical and transport properties. Free energy calculations show that a single-layer form, termed green phosphorene, is energetically more stable than blue phosphorene and a phase transition from black to green phosphorene can occur at temperatures above 87 K. Due to its buckled structure, green phosphorene can be synthesized on corrugated metal surfaces rather than clean surfaces.The successful isolation of graphene [1], a single layer of carbon atoms in a two-dimensional (2D) honeycomb lattice, has generated tremendous interest in 2D layered materials [2]. Various applications using graphene have been explored based on the unusual properties such as massless Dirac fermions, high mobility, and high thermal conductivity [3,4]. However, the gapless nature of graphene has been an obstacle in practical applications for electronic devices due to its low on/off ratios [5]. Transition metal dichalcogenides belonging to the family of 2D materials have the semiconducting gaps in the visible range, but the carrier mobility in thin films is significanlty reduced [6]. Recently, atomically thin black phosphorus has been successfully separated from its layered bulk [7,8], and this emerging 2D material with the tunable band gap by varying the number of atomic layers bridges the gap between graphene and transition metal dichalcogenides [9,10]. Due to its high anisotropic mobility, black phosphorus is considered as a promising material for electronic and optoelectronic devices [6-8, 11, 12].Elemental phosphorus is known to exist in several three-dimensional (3D) allotropes, such as red, white, and violet phosphorus, besides black phosphorus (α-P) which is the most stable phase among them. Due to the presence of various phases, it is expected that an unknown phosphorus allotrope will form under the control of substrate, temperature, and pressure. Zhu and Tománek proposed a new stable phase of phosphorus called blue phosphorus (β-P), with the structural similarity to a buckled graphene [13]. Unlike black phosphorus, blue phosphorus displays the indirect band gaps, regardless of the number of atomic layers. Other 2D structures such as γ-, δ-, ε-, ζ-, η-, θ-, and ψ-phosphorene were later suggested based on theoretical calculations [14][15][16][17][18]. Recently, blue phosphorene has been successfully synthesized on the Au(111) substrate by molecular beam epitaxy [19]. The realization of blue phosphorene not only opens up the potential of various metastable allotropes but also motivates research into a new level of phosphorus that provides exciting characteristics such as broad band gaps and high anisotropic mobility.In this work, we use an ab initio evolutionary crystal structure search method to explore a new phosphorus allotrope called green phosphorus. The new P allotrope belongs to a class of 2D material...

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supporting

confidence: 82%

Prediction of Green Phosphorus with Tunable Direct Band Gap and High Mobility

Han

Kim

Lee

et al. 2017

J. Phys. Chem. Lett.

108

102

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“…To point out the changing stability order of the Pn = P, As crystal structures, calculations were perfomed on orthorhombic and trigonal layered structures of P and As [3,4]. Similar to our earlier work on TN 2 (T = C, Si, Ge) compounds [65], calculations with the LDA functional underestimate lattice parameters, which are mostly overestimated by the GGA.…”

Section: Resultsmentioning

confidence: 99%

“…This agrees well with a comprehensive investigation [23] that predicted the building units of Hittorf's (and fibrous) phosphorus as energetically most favorable of all predicted tubular phosphorus chains. That paper also described the energetic order of the nanorod fragments with rising stability from [P8]P4 (4) [4]), the energy gain for rod packing, i.e., the amount of van der Waals bonding interaction between the tubes, gets lower in this row, and therefore the energetic order must be modified accordingly. While the description of the tubular structures per se is fairly consistent for the different functionals, relative energy differences between the other allotropes disagree significantly.…”

Section: Resultsmentioning

confidence: 99%

“…One part of the project dealt with the relative stabilities of polymorphs of dipnictides NiPn 2 (Pn = N, P, As, Sb, Bi) [1] and related ternary ordering variants MPnS (M = Fe, Co, Ni; Pn = As, Sb) [2]. The structures of the pnictogen elements themselves were studied in another part of the project with a focus on the solid solution As x P 1-x [3] and the various allotropes of phosphorus [4]. Subsequently, some of the well-known and new phosphorus allotropes have been thoroughly investigated concerning the role of van der Waals interactions for their solid structures and relative stabilities.…”

Section: Introductionmentioning

confidence: 99%

“…The phosphorus allotropes serve as a benchmark case to study the performance of standard levels of DFT on lowdimensional systems with strong covalent networks that are interconnected by van der Waals forces. The latter turned out to be evident for the correct description of the entire stability range, solid structures, and the prediction of the crystal structures of the recently discovered P nanorod allotropes [4]. The results are evaluated in more detail herein with supplementary material and a focus on the applied methods and the treatment of dispersive interactions.…”

Section: Introductionmentioning

confidence: 99%

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Van der Waals interactions in selected allotropes of phosphorus

Bachhuber

Appen

Dronskowski

et al. 2014

Zeitschrift Für Kristallographie - Crystalline Materials

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Selected allotropes of phosphorus are investigated by different levels of density functional theory (DFT) calculations to evaluate the relative stability orders with a special focus on the role of van der Waals interactions. Phosphorus is an excellent reference system with a large number of allotropes. Starting from low-dimensional molecular (0D, white P) and polymer structures (1D, P nanorods) to layered (2D, black P) and tubular structures (2D and 3D, crystalline forms of red P), covalent structure motifs are interconnected by van der Waals interactions. They are a key factor for the correct energetic description of all P allotropes. A comparative study is carried out within the local density approximation (LDA) and the generalized gradient approximation (GGA), with and without implementation of a dispersion correction by Grimme (GGA-D2). Our intention is to achieve a reasonable agreement of our calculations with experimental data, the plausibility of energy values, and the treatment of long-range interactions. The effect of van der Waals interactions is exemplified for the interlayer distances of black phosphorous and its electronic structure.

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Introduction to the Energetics and Thermochemical Aspects of Polynitrogen Species

Slayden

Greer

Liebman

2019

Patai's Chemistry of Functional Groups

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In this chapter, we present some known, established rules, regularities, and observations in the thermochemistry of nitrogen and its compounds. Comparison of the enthalpies of formation and bond strengths are a main focus of the discussion. We also present new patterns and regularities, making comparisons with related compounds of other elements as a way of introducing diverse classes of compounds. We also discuss the trivial names of acyclic and heterocyclic compounds containing multiple nitrogens and document species with nitrogen–nitrogen bonds that have been often ignored by the chemical community. Consequences of the weakness of the nitrogen–nitrogen single bonds are explicitly mentioned.

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The Extended Stability Range of Phosphorus Allotropes

Cited by 154 publications

References 52 publications

Prediction of Green Phosphorus with Tunable Direct Band Gap and High Mobility

Prediction of Green Phosphorus with Tunable Direct Band Gap and High Mobility

Van der Waals interactions in selected allotropes of phosphorus

Introduction to the Energetics and Thermochemical Aspects of Polynitrogen Species

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