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Intrinsic defects, fluctuations of the local shape, and the photo-oxidation of black phosphorus  [PDF]
Kainen L. Utt,Pablo Rivero,Mehrshad Mehboudi,Edmund O. Harriss,Mario F. Borunda,Alejandro A. Pacheco SanJuan,Salvador Barraza-Lopez
Physics , 2015,
Abstract: Black phosphorus is a monoatomic semiconducting layered material that degrades exothermically in the presence of light and ambient contaminants. Its degradation dynamics remain largely unknown. Even before degradation, local-probe studies indicate non-negligible local curvature --through a non-constant height distribution-- due to the unavoidable presence of intrinsic defects. We establish that these intrinsic defects are photo-oxidation sites because they lower the chemisorption barrier of ideal black phosphorus (> 10 eV and out of visible-range light excitations) right into the visible and ultra-violet range (1.6 to 6.8 eV), thus enabling photo-induced oxidation and dissociation of oxygen dimers. A full characterization of the material's shape and of its electronic properties at the early stages of the oxidation process is presented as well. This study thus provides fundamental insights into the degradation dynamics of this novel layered material.
Two-Dimensional Magnetotransport in a Black Phosphorus Naked Quantum Well  [PDF]
V. Tayari,N. Hemsworth,I. Fakih,A. Favron,E. Gaufrès,G. Gervais,R. Martel,T. Szkopek
Physics , 2014, DOI: 10.1038/ncomms8702
Abstract: Black phosphorus (bP) is the second known elemental allotrope with a layered crystal structure that can be mechanically exfoliated down to atomic layer thickness. We have fabricated bP naked quantum wells in a back-gated field effect transistor geometry with bP thicknesses ranging from $6\pm1$ nm to $47\pm1$ nm. Using an encapsulating polymer superstrate, we have suppressed bP oxidation and have observed field effect mobilities up to 600 cm$^2$/Vs and on/off current ratios exceeding $10^5$. Importantly, Shubnikov-de Haas (SdH) oscillations observed in magnetotransport measurements up to 35 T reveal the presence of a 2-D hole gas with Schr\"odinger fermion character in an accumulation layer at the bP/oxide interface. Our work demonstrates that 2-D electronic structure and 2-D atomic structure are independent. 2-D carrier confinement can be achieved in layered semiconducting materials without necessarily approaching atomic layer thickness, advantageous for materials that become increasingly reactive in the few-layer limit such as bP.
Environmental, Thermal, and Electrical Susceptibility of Black Phosphorus Field Effect Transistors  [PDF]
Zenghui Wang,Arnob Islam,Rui Yang,Xu-Qian Zheng,Philip X. -L. Feng
Physics , 2015,
Abstract: Atomic layers of black phosphorus (P) isolated from its layered bulk make a new two-dimensional (2D) semiconducting crystal with sizable direct bandgap, high carrier mobility, and promises for 2D electronics and optoelectronics. However, the integrity of black P crystal could be susceptible to a number of environmental variables and processes, resulting in degradation in device performance even before the device optical image suggests so. Here, we perform a systematic study of the environmental effects on black P electronic devices through continued measurements over a month under a number of controlled conditions, including ambient light, air, and humidity, and identify evolution of device performance under each condition. We further examine effects of thermal and electrical treatments on inducing morphology and, performance changes and failure modes in black P devices. The results suggest that procedures well established for nanodevices in other 2D materials may not directly apply to black P devices, and improved procedures need to be devised to attain stable device operation.
Anomalous Quantum Transport Properties in Semimetallic Black Phosphorus  [PDF]
Kazuto Akiba,Astushi Miyake,Yuichi Akahama,Kazuyuki Matsubayashi,Yoshiya Uwatoko,Hayato Arai,Yuki Fuseya,Masashi Tokunaga
Physics , 2015, DOI: 10.7566/JPSJ.84.073708
Abstract: Magnetoresistance in single crystals of black phosphorus is studied at ambient and hydrostatic pressures. In the semiconducting states at pressures below 0.71 GPa, the magnetoresistance shows periodic oscillations, which can be ascribed to the magneto-phonon resonance that is characteristic of high mobility semiconductors. In the metallic state above 1.64 GPa, the both transverse and longitudinal magnetoresistance show titanic increase with exhibiting superposed Shubnikov-de Haas oscillations. The observed small Fermi surfaces, high mobilities and light effective masses of carriers in semimetallic black phosphorus are comparable to those in the representative elemental semimetals of bismuth and graphite.
Electric field effect in ultrathin black phosphorus  [PDF]
Steven P. Koenig,Rostislav A. Doganov,Hennrik Schmidt,A. H. Castro Neto,Barbaros Oezyilmaz
Physics , 2014, DOI: 10.1063/1.4868132
Abstract: Black phosphorus exhibits a layered structure similar to graphene, allowing mechanical exfoliation of ultrathin single crystals. Here we demonstrate few-layer black phosphorus field effect devices on Si/SiO$_2$ and measure charge carrier mobility in a four-probe configuration as well as drain current modulation in a two-point configuration. We find room-temperature mobilities of up to 300 cm$^2$/Vs and drain current modulation of over 10$^3$. At low temperatures the on-off ratio exceeds 10$^5$ and the device exhibits both electron and hole conduction. Using atomic force microscopy we observe significant surface roughening of thin black phosphorus crystals over the course of 1 hour after exfoliation.
Dual gate black phosphorus velocity modulated transistor  [PDF]
V. Tayari,N. Hemsworth,O. Cyr-Choinière,W. Dickerson,G. Gervais,T. Szkopek
Physics , 2015,
Abstract: The layered semiconductor black phosphorus has attracted attention as a 2D atomic crystal that can be prepared in ultra-thin layers for operation as field effect transistors. Despite the susceptibility of black phosphorus to photo-oxidation, improvements to the electronic quality of black phosphorus devices has culminated in the observation of the quantum Hall effect. In this work, we demonstrate the room temperature operation of a dual gated black phosphorus transistor operating as a velocity modulated transistor, whereby modification of hole density distribution within a black phosphorus quantum well leads to a two-fold modulation of hole mobility. Simultaneous modulation of Schottky barrier resistance leads to a four-fold modulation of transcon- ductance at a fixed hole density. Our work explicitly demonstrates the critical role of charge density distribution upon charge carrier transport within 2D atomic crystals.
The Renaissance of Black Phosphorus  [PDF]
Xi Ling,Han Wang,Shengxi Huang,Fengnian Xia,Mildred Dresselhaus
Physics , 2015, DOI: 10.1073/pnas.1416581112
Abstract: 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 two-dimensional (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 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.
Mobility anisotropy in monolayer black phosphorus due to charged impurities  [PDF]
Yue Liu,Tony Low,P. Paul Ruden
Physics , 2015,
Abstract: We study the charged impurity limited mobility in black phosphorus, a highly anisotropic layered material. We compute the mobility within the Boltzmann transport equation under detailed balance condition, and taking into account the anisotropy in transport and electronic structure. For carrier densities accessible in experiments, we obtained an anisotropy ratio of 3 ~ 4 at zero temperature, two-folds larger than that observed in experiments on multilayers samples. We discuss also how the anisotropy depends on carrier density and impurity distribution.
Multilayer black phosphorus as broadband saturable absorber for pulsed lasers from 1 to 2.7 μm wavelength  [PDF]
Lingchen Kong,Zhipeng Qin,Guoqiang Xie,Zhinan Guo,Han Zhang,Peng Yuan,Liejia Qian
Physics , 2015,
Abstract: It attracts wide interest to seek universe saturable absorber covering wavelengths from near infrared to mid-infrared band. Multilayer black phosphorus, with variable direct bandgap (0.3-2 eV) depending on the layer number, becomes a good alternative as a universe saturable absorber for pulsed lasers. In this contribution, we first experimentally demonstrated broadband saturable absorption of multilayer black phosphorus from 1 {\mu}m to 2.7 {\mu}m wavelength. With the as-fabricated black phosphorus nanoflakes as saturable absorber, stable Q-switching operation of bulk lasers at 1.03 {\mu}m, 1.93 {\mu}m, 2.72 {\mu}m were realized, respectively. In contrast with large-bandgap semiconducting transition metal dichalcogenides, such as MoS2, MoSe2, multilayer black phosphorus shows particular advantage at the long wavelength regime thanks to its narrow direct bandgap. This work will open promising optoelectronic applications of black phosphorus in mid-infrared spectral region and further demonstrate that BP may fill the gap of between zero-bandgap graphene and large-bandgap TMDs.
Simulated scanning tunneling microscopy images of few-layer-phosphorus capped by graphene and hexagonal boron nitride monolayers  [PDF]
Pablo Rivero,Cedric M. Horvath,Zhen Zhu,Jie Guan,David Tománek,Salvador Barraza-Lopez
Physics , 2014, DOI: 10.1103/PhysRevB.91.115413
Abstract: Elemental phosphorous is believed to have several stable allotropes that are energetically nearly degenerate, but chemically reactive. To prevent chemical degradation under ambient conditions, these structures may be capped by monolayers of hexagonal boron nitride ({\em h}-BN) or graphene. We perform {\em ab initio} density functional calculations to simulate scanning tunneling microscopy (STM) images of different layered allotropes of phosphorus and study the effect of capping layers on these images. We find that protective monolayers of insulating {\em h}-BN allow to distinguish between the different structural phases of phosphorus underneath, even though the images are filtered through only nitrogen atoms that appear transparent. No such distinction is possible for phosphorus films capped by semimetallic graphene that masks the underlying structure. Our results suggest that the real-space imaging capability of STM is not hindered by selected capping layers that protect phosphorus surfaces.
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