One hundred years after its first successful synthesis in the bulk form in 1914, black phosphorus (black P) was recently rediscovered from the perspective of a 2D layered material, attracting tremendous interest from condensed matter physicists, chemists, semiconductor device engineers, and material scientists. Similar to graphite and transition metal dichalcogenides (TMDs), black P has a layered structure but with a unique puckered single-layer geometry. Because the direct electronic band gap of thin film black P can be varied from 0.3 eV to around 2 eV, depending on its film thickness, and because of its high carrier mobility and anisotropic in-plane properties, black P is promising for novel applications in nanoelectronics and nanophotonics different from graphene and TMDs. Black P as a nanomaterial has already attracted much attention from researchers within the past year. Here, we offer our opinions on this emerging material with the goal of motivating and inspiring fellow researchers in the 2D materials community and the broad readership of PNAS to discuss and contribute to this exciting new field. We also give our perspectives on future 2D and thin film black P research directions, aiming to assist researchers coming from a variety of disciplines who are desirous of working in this exciting research field.

https://www.pnas.org/content/pnas/112/15/4523.full.pdf

The renaissance of black phosphorus

Phosphorus is one of the most abundant elements preserved in earth, constructing with a fraction of ~0.1% of the earth crust. In general, phosphorus has several allotropes. The two most commonly seen allotropes, white and red phosphorus, are widely used in explosives and safety matches. In addition, black phosphorus, though rarely mentioned, is a layered semiconductor and have great potentials in optical and electronic applications. Remarkably, this layered material can be reduced to one single atomic layer in the vertical direction owing to the van der Waals structure, known as phosphorene, where the physical properties can be tremendously different from its bulk counterpart. In this review article, we trace back to the 100 years research history on black phosphorus from the synthesis to material properties, and extend the topic from black phosphorus to phosphorene. The physical and transport properties are highlighted, aiming at further applications in electronic and optoelectronics devices.

Semiconducting Black Phosphorus: Synthesis, Transport Properties and Electronic Applications

Phosphorene, an emerging two-dimensional material, has received considerable attention due to its layer-controlled direct bandgap, high carrier mobility, negative Poisson's ratio and unique in-plane anisotropy. As cousins of phosphorene, 2D group-VA arsenene, antimonene and bismuthene have also garnered tremendous interest due to their intriguing structures and fascinating electronic properties. 2D group-VA family members are opening up brand-new opportunities for their multifunctional applications encompassing electronics, optoelectronics, topological spintronics, thermoelectrics, sensors, Li- or Na-batteries. In this review, we extensively explore the latest theoretical and experimental progress made in the fundamental properties, fabrications and applications of 2D group-VA materials, and offer perspectives and challenges for the future of this emerging field.

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Recent progress in 2D group-VA semiconductors: from theory to experiment

The recent isolation of atomically thin black phosphorus by mechanical exfoliation of bulk layered crystals has triggered an unprecedented interest, even higher than that raised by the first works on graphene and other two-dimensionals, in the nanoscience and nanotechnology community. In this Perspective, we critically analyze the reasons behind the surge of experimental and theoretical works on this novel two-dimensional material. We believe that the fact that black phosphorus band gap value spans over a wide range of the electromagnetic spectrum (interesting for thermal imaging, thermoelectrics, fiber optics communication, photovoltaics, etc.) that was not covered by any other two-dimensional material isolated to date, its high carrier mobility, its ambipolar field-effect, and its rather unusual in-plane anisotropy drew the attention of the scientific community toward this two-dimensional material. Here, we also review the current advances, the future directions and the challenges in this young research...

Black Phosphorus: Narrow Gap, Wide Applications

Phosphorene, the single- or few-layer form of black phosphorus, was recently rediscovered as a two-dimensional layered material holding great promise for applications in electronics and optoelectronics. Research into its fundamental properties and device applications has since seen exponential growth. In this Perspective, we review recent progress in phosphorene research, touching upon topics on fabrication, properties, and applications; we also discuss challenges and future research directions. We highlight the intrinsically anisotropic electronic, transport, optoelectronic, thermoelectric, and mechanical properties of phosphorene resulting from its puckered structure in contrast to those of graphene and transition-metal dichalcogenides. The facile fabrication and novel properties of phosphorene have inspired design and demonstration of new nanodevices; however, further progress hinges on resolutions to technical obstructions like surface degradation effects and nonscalable fabrication techniques. We also briefly describe the latest developments of more sophisticated design concepts and implementation schemes that address some of the challenges in phosphorene research. It is expected that this fascinating material will continue to offer tremendous opportunities for research and development for the foreseeable future.

Phosphorene: Fabrication, Properties, and Applications.

Phosphorene, the single layer counterpart of black phosphorus, is a novel two-dimensional semiconductor with high carrier mobility and a large fundamental direct band gap, which has attracted tremendous interest recently. Its potential applications in nano-electronics and thermoelectrics call for fundamental study of the phonon transport. Here, we calculate the intrinsic lattice thermal conductivity of phosphorene by solving the phonon Boltzmann transport equation (BTE) based on first-principles calculations. The thermal conductivity of phosphorene at 300 K is 30.15 W m−1 K−1 (zigzag) and 13.65 W m−1 K−1 (armchair), showing an obvious anisotropy along different directions. The calculated thermal conductivity fits perfectly to the inverse relationship with temperature when the temperature is higher than Debye temperature (ΘD = 278.66 K). In comparison to graphene, the minor contribution around 5% of the ZA mode is responsible for the low thermal conductivity of phosphorene. In addition, the representative mean free path (MFP), a critical size for phonon transport, is also obtained.

Anisotropic intrinsic lattice thermal conductivity of phosphorene from first principles

We systematically investigated the geometric, electronic and thermoelectric (TE) properties of bulk black phosphorus (BP) under strain. The hinge-like structure of BP brings unusual mechanical responses such as anisotropic Young's modulus and negative Poisson's ratio. A sensitive electronic structure of BP makes it transform among metal, direct and indirect semiconductors under strain. The maximal figure of merit ZT of BP is found to be 0.72 at 800 K that could be enhanced to 0.87 by exerting an appropriate strain, revealing BP could be a potential medium-high temperature TE material. Such strain-induced enhancements of TE performance are often observed to occur at the boundary of the direct-indirect band gap transition, which can be attributed to the increase of degeneracy of energy valleys at the transition point. By comparing the structure of BP with SnSe, a family of potential TE materials with hinge-like structure are suggested. This study not only exposes various novel properties of BP under strain, but also proposes effective strategies to seek for better TE materials.

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Hinge-like structure induced unusual properties of black phosphorus and new strategies to improve the thermoelectric performance

New classes of two-dimensional (2D) materials beyond graphene, including layered and non-layered, and their heterostructures, are currently attracting increasing interest due to their promising applications in nanoelectronics, optoelectronics and clean energy, where thermal transport is a fundamental physical parameter. In this paper, we systematically investigated the phonon transport properties of the 2D orthorhombic group IV–VI compounds of GeS, GeSe, SnS and SnSe by solving the Boltzmann transport equation (BTE) based on first-principles calculations. Despite their similar puckered (hinge-like) structure along the armchair direction as phosphorene, the four monolayer compounds possess diverse anisotropic properties in many aspects, such as phonon group velocity, Young's modulus and lattice thermal conductivity (κ), etc. Especially, the κ along the zigzag and armchair directions of monolayer GeS shows the strongest anisotropy while monolayer SnS and SnSe show almost isotropy in phonon transport. The origin of the diverse anisotropy is fully studied and the underlying mechanism is discussed in details. With limited size, the κ could be effectively lowered, and the anisotropy could be effectively modulated by nanostructuring, which would extend the applications to nanoscale thermoelectrics and thermal management. Our study offers fundamental understanding of the anisotropic phonon transport properties of 2D materials, and would be of significance for further study, modulation and applications in emerging technologies.

Diverse anisotropy of phonon transport in two-dimensional group IV-VI compounds: A comparative study.

Two-dimensional (2D) materials with graphene as a representative have been intensively studied for a long time. Recently, monolayer gallium nitride (ML GaN) with honeycomb structure was successfully fabricated in experiments, generating enormous research interest for its promising applications in nano- and opto-electronics. Considering all these applications are inevitably involved with thermal transport, systematic investigation of the phonon transport properties of 2D GaN is in demand. In this paper, by solving the Boltzmann transport equation (BTE) based on first-principles calculations, we performed a comprehensive study of the phonon transport properties of ML GaN, with detailed comparison to bulk GaN, 2D graphene, silicene and ML BN with similar honeycomb structure. Considering the similar planar structure of ML GaN to graphene, it is quite intriguing to find that the thermal conductivity (κ) of ML GaN (14.93 W mK-1) is more than two orders of magnitude lower than that of graphene and is even lower than that of silicene with a buckled structure. Systematic analysis is performed based on the study of the contribution from phonon branches, comparison among the mode level phonon group velocity and lifetime, the detailed process and channels of phonon-phonon scattering, and phonon anharmonicity with potential energy well. We found that, different from graphene and ML BN, the phonon-phonon scattering selection rule in 2D GaN is slightly broken by the lowered symmetry due to the large difference in the atomic radius and mass between Ga and N atoms. Further deep insight is gained from the electronic structure. Resulting from the special sp orbital hybridization mediated by the Ga-d orbital in ML GaN, the strongly polarized Ga-N bond, localized charge density, and its inhomogeneous distribution induce large phonon anharmonicity and lead to the intrinsic low κ of ML GaN. The orbitally driven low κ of ML GaN unraveled in this work would make 2D GaN prospective for applications in energy conversion such as thermoelectrics. Our study offers fundamental understanding of phonon transport in ML GaN within the framework of BTE and further electronic structure, which will enrich the studies of nanoscale phonon transport in 2D materials and shed light on further studies.

Orbitally driven low thermal conductivity of monolayer gallium nitride (GaN) with planar honeycomb structure: a comparative study

New classes two-dimensional (2D) materials beyond graphene, including layered and non-layered, and their heterostructures, are currently attracting increasing interest due to their promising applications in nanoelectronics, optoelectronics and clean energy, where thermal transport property is one of the fundamental physical parameters. In this paper, we systematically investigated the phonon transport properties of 2D orthorhombic group IV-VI compounds of $GeS$, $GeSe$, $SnS$ and $SnSe$ by solving the Boltzmann transport equation (BTE) based on first-principles calculations. Despite the similar puckered (hinge-like) structure along the armchair direction as phosphorene, the four monolayer compounds possess diverse anisotropic properties in many aspects, such as phonon group velocity, Young's modulus and lattice thermal conductivity ($\kappa$), etc. Especially, the $\kappa$ along the zigzag and armchair directions of monolayer $GeS$ shows the strongest anisotropy while monolayer $SnS$ and $SnSe$ shows an almost isotropy in phonon transport. The origin of the diverse anisotropy is fully studied and the underlying mechanism is discussed in detail. With limited size, the $\kappa$ could be effectively lowered, and the anisotropy could be effectively modulated by nanostructuring, which would extend the applications in nanoscale thermoelectrics and thermal management. Our study offers fundamental understanding of the anisotropic phonon transport properties of 2D materials, and would be of significance for further study, modulation and aplications in emerging technologies.

Zhenzhen Qin

Papers

Anisotropic intrinsic lattice thermal conductivity of phosphorene from first principles

Hinge-like structure induced unusual properties of black phosphorus and new strategies to improve the thermoelectric performance

Diverse anisotropy of phonon transport in two-dimensional group IV-VI compounds: A comparative study.

Orbitally driven low thermal conductivity of monolayer gallium nitride (GaN) with planar honeycomb structure: a comparative study

Diverse anisotropy of phonon transport in two-dimensional IV-VI compounds: A comparative study