Phosphorene Layers Research Articles

Twisted bilayer blue phosphorene: A direct band gap semiconductor

We report that two rotated layers of blue phosphorene behave as a direct band gap semiconductor. The optical spectrum shows absorption peaks in the visible region of the spectrum and in addition the energy of these peaks can be tuned with the rotational angle. These findings makes twisted bilayer blue phosphorene a strong candidate as a solar cell or photodetection device. Our results are based on ab initio calculations of several rotated blue phosphorene layers.

Heterostructured hBN-BP-hBN Nanodetectors at Terahertz Frequencies.

By reassembling thin isolated atomic planes of hexagonal borum nitride (hBN) with a few layer phosphorene black phosphorus (BP), hBN/BP/hBN heterostructures are mechanically stacked to devise high-efficiency THz photodetectors operating in the 0.3-0.65 THz range, from 4 K to 300 K, with a record signal-to-noise ratio of 20 000.

Design strategy of two-dimensional material field-effect transistors: Engineering the number of layers in phosphorene FETs

Thickness or the number of layers in 2D semiconductors is a key parameter to determine the material's electronic properties and the overall device performance of 2D material electronics. Here, we discuss the engineering practice of optimizing material and device parameters of phosphorene field-effect transistors (FETs) by means of self-consistent atomistic quantum transport simulations, where the impacts of different numbers of phosphorene layers on various device characteristics are explored in particular, considering two specific target applications of high-performance and low-power devices. Our results suggest that, for high-performance applications, monolayer phosphorene should be utilized in a conventional FET structure since it can provide the equally large on current as other multilayer phosphorenes (Ion > 1 mA/μm) without showing a penalty of relatively lower density of states, along with favorableness for steep switching and large immunity to gate-induced drain leakage. On the other hand, more comprehensive approach is required for low-power applications, where operating voltage, doping concentration, and channel length should be carefully engineered along with the thickness of phosphorene in tunnel FET (TFET) structure to achieve ultra-low leakage current without sacrificing on current significantly. Our extensive simulation results revealed that either bilayer or trilayer phosphorene can provide the best performance in TFET with the maximum Ion/Ioff of ∼2 × 1011 and the subthreshold swing as low as 13 mV/dec. In addition, our comparative study of phosphorene-based conventional FET and TFET clearly shows the feasibility and the limitation of each device for different target applications, providing irreplaceable insights into the design strategy of phosphorene FETs that can be also extended to other similar layered material electronic devices.

Thickness and electric-field-dependent polarizability and dielectric constant in phosphorene

Based on extensive first principle calculations, we explore the thickness dependent effective di- electric constant and slab polarizability of few layer black phosphorene. We find that the dielectric constant in ultra-thin phosphorene is thickness dependent and it can be further tuned by applying an out of plane electric field. The decreasing dielectric constant with reducing number of layers of phosphorene, is a direct consequence of the lower permittivity of the surface layers and the in- creasing surface to volume ratio. We also show that the slab polarizability depends linearly on the number of layers, implying a nearly constant polarizability per phosphorus atom. Our calculation of the thickness and electric field dependent dielectric properties will be useful for designing and interpreting transport experiments in gated phosphorene devices, wherever electrostatic effects such as capacitance, charge screening etc. are important.

(Invited) Synthesis and Growth of the Phosphorene Precursor Black Phosphorus

Black phosphorus and the 2D monolayer material called phosphorene gained reasonable interest in the past two years. Due to the structural anisotropy and the non-vanishing band gap few layer phosphorene and monolayer phosphorene are potential candidate for semiconductor, sensor and optical applications. Herein we will present a brief overview on the synthesis and growth of black phosphorus, the precursor material for phosphorene. A short range vapor transport results in the effective synthesis of large, high quality black phosphorus crystals which can be easily delaminated afterwards. This principle is commonly used to produce this allotrope in industry and academia. In situ experiments using neutrons have been performed to follow the growth of black phosphorus. A growing principle has been derived from isothermal measurements and an upper and lower synthesis temperature has been determined. We will present some applications of phosphorene and doped phosphorene thin-layer materials prepared by the above mentioned approach. After a short and brief overview on theoretically predicted and realized aspects and applications of phosphorus and phosphorene chemistry, we will try to compare this outcome with other 2D materials in the field.

(Invited) Controlling the Band Structure of Black Phosphorus

Two-dimensional (2D) atomic crystals have emerged as a class of materials that may impact our future electronics technology [1]. A key issue is controlling their electronic state to overcome the limit of natural properties. In this regard, there are rapidly growing interests in black phosphorus, a layered material consisting of 2D phosphorene layers. The low-energy band structure of black phosphorus has been widely predicted to be tunable by external perturbations, such as applied strain and electric field [2]. In this talk, I will introduce our recent angle-resolved photoemission spectroscopy studies on the tunable band gap of black phosphorus. By the in-situdeposition of alkali-metal atoms on the surface of black phosphorus, we found that the vertical electric field from dopants modulates the band gap, and changes the material from a narrow-gap semiconductor to a band-overlapped semimetal [3]. At the critical density of this semiconductor-semimetal transition, the material becomes a 2D Dirac semimetal, whose band dispersion is highly anisotropic, linear in armchair and quadratic in zigzag directions [3]. [1] E. S. Reich, Nature 506, 19 (2014). [2] H. O. H. Churchill and P. Jarillo-Herrero, Nature Nanotech. 9, 330 (2014). [3] J. Kim, S. S. Baek, S. H. Ryu, Y. Sohn, S. Park, B. G. Park, J. D. Denlinger, Y. Yi, H. J. Choi, and K. S. Kim, Science 349, 723 (2015).

Optical reflection, transmission and absorption properties of single-layer black phosphorus from a model calculation

An effective anisotropic tight-binding model is developed to analytically describe the low-energy electronic structure and optical response of phosphorene (a black phosphorus (BP) monolayer). Within the framework of the model, we derive explicit closed-form expressions, in terms of elementary functions, for the elements of the optical conductivity tensor of phosphorene. These relations provide a convenient parametrization of the highly anisotropic optical response of phosphorene, which allows the reflectance, transmittance, and absorbance of this material to be easily calculated as a function of the frequency of the incident radiation at arbitrary angles of incidence. The results of such a calculation are presented for both a free-standing phosphorene layer and the phosphorene layer deposited on a substrate, and for the two principal cases of polarization of the incident radiation either parallel to or normal to the plane of incidence. Our findings (e.g., a ‘quasi-Brewster’ effect in the reflectance of the phosphorene/ overlayer system) pave the way for developing a new, purely optical method of distinguishing BP monolayers.

Characterization and sonochemical synthesis of black phosphorus from red phosphorus

Phosphorene is a new two-dimensional material which is commonly prepared by exfoliation from black phosphorus bulk crystals that historically have been synthesized from white phosphorus under high-pressure conditions. The few layers of phosphorene have a direct band gap in the range of 0.3–2 eV and high mobility at room temperature comparable to epitaxial graphene. These characteristics can be used for the design of high speed digital circuits, radio frequency circuits, flexible and printed systems, and optoelectronic devices. In this work, we synthesized black phosphorus from red phosphorus, which is a safer solid precursor, using sonochemistry. Furthermore, via a variety of microscopy and spectroscopy techniques, we report characterization results of the sonochemically synthesized black phosphorus in addition to the commercial black phosphorus. Finally, we describe the air stability of black phosphors and the crystalline structure of the synthesized material. This is the first result of sonochemical or solution-based synthesis of black phosphorus based on readily available low-cost red phosphorus. This solution-based synthesis of black phosphorus is suitable for printable applications of nanomaterial.

Manipulation of n and p type dope black phosphorene layer: A first principles study

We investigated the physical properties of the semiconducting impurity (Ga, Ge, As, and Se) doped phosphorene layer systems. The Ga and As doped layer showed a semiconducting behavior while the Ge doped system displayed a metallic state. The magnetic state appeared in the Se doped phosphorene. Deep donor or acceptor sates was found with doping of semiconducting impurities. To investigate an effective n and p type doped phosphorene, we explored the charge carrier doping effect. With an external electron carrier doping, the donor level induced by the Se impurity became an effective shallow donor level. Due to the Fermi level shifting, the metallic to semiconductor or vice versa was found in Ge and As. For external hole carrier doping, all the systems showed metallic band structures except for the Se doped structure. The Se impurity created a shallow acceptor state with an extra hole. Particularly, we propose that the most promising dopant is the Se because it creates a magnetic state in phosphorene and an extra electron or hole doping can induce an n-type or p-type phosphorene respectively. This suggests that the Se doped phosphorene has potential applications for both dilute magnetic semiconductor and p–n junction device applications.

Long-Range Magnetic Ordering and Switching of Magnetic State by Electric Field in Porous Phosphorene.

We explored the possibility of long-range magnetic ordering in two-dimensional porous phosphorene (PP) layer by means of ab-initio calculations. The self-passivated pore geometry showed a nonmagnetic state while the pore geometry with dangling bond at two zigzag edges with a distance of 7.7 Å preferred an antiferromagnetic ordering (AFM). Pore to pore magnetic interaction with a distance of 13.5 Å between two pores was found to be remarkably long ranged, and this emerges from the interactions between the magnetic tails of the edge states in the armchair direction. The AFM state was persisted by the oxidation of the edge. Interestingly, the long-range AFM ordering changed to long-range ferromagnetic (FM) ordering by external electric field. The results are noteworthy in the interplay between electric field and electronic spin degree of freedom in phosphorene studies and may also open a promising way to explore phosphorene-based spintronics devices.

Surface structure determination of black phosphorus using photoelectron diffraction

The atomic structure of single-crystalline black phosphorus is studied using high-resolution synchrotron-based photoelectron diffraction (XPD). The results show that the topmost phosphorene layer in the black phosphorus is slightly displaced compared to the bulk structure and presents a small contraction in the direction perpendicular to the surface. Furthermore, the XPD results show the presence of a small buckling among the surface atoms, in agreement with previously reported scanning tunneling microscopy results. The contraction of the surface layer added to the presence of the buckling indicates a uniformity in the size of the $s{p}^{3}$ bonds between P atoms at the surface.

First principles calculations of solid-state thermionic transport in layered van der Waals heterostructures.

This work aims at understanding solid-state energy conversion and transport in layered (van der Waals) heterostructures in contact with metallic electrodes via a first-principles approach. As an illustration, a graphene/phosphorene/graphene heterostructure in contact with gold electrodes is studied by using density functional theory (DFT)-based first principles calculations combined with real space Green's function (GF) formalism. We show that for a monolayer phosphorene, quantum tunneling dominates the transport. By adding more phosphorene layers, one can switch from tunneling-dominated transport to thermionic-dominated transport, resulting in transporting more heat per charge carrier, thus, enhancing the cooling coefficient of performance. The use of layered van der Waals heterostructures has two advantages: (a) thermionic transport barriers can be tuned by changing the number of layers, and (b) thermal conductance across these non-covalent structures is very weak. The phonon thermal conductance of the present van der Waals heterostructure is found to be 4.1 MW m(-2) K(-1) which is one order of magnitude lower than the lowest value for that of covalently-bonded interfaces. The thermionic coefficient of performance for the proposed device is 18.5 at 600 K corresponding to an equivalent ZT of 0.13, which is significant for nanoscale devices. This study shows that layered van der Waals structures have great potential to be used as solid-state energy-conversion devices.

A comparative first-principles study of the lithiation, sodiation, and magnesiation of black phosphorus for Li-, Na-, and Mg-ion batteries.

Using first-principles calculations, we describe and compare atomistic lithiation, sodiation, and magnesiation processes in black phosphorous with a layered structure similar to graphite for Li-, Na-, and Mg-ion batteries because graphite is not considered to be an electrode material for Na- and Mg-ion batteries. The three processes are similar in that an intercalation mechanism occurs at low Li/Na/Mg concentrations, and then further insertion of Li/Na/Mg leads to a change from the intercalation mechanism to an alloying process. Li and Mg show a columnar intercalation mechanism and prefer to locate in different phosphorene layers, while Na shows a planar intercalation mechanism and preferentially localizes in the same layer. In addition, we compare the mechanical properties of black phosphorous during lithiation, sodiation, and magnesiation. Interestingly, lithiation and sodiation at high concentrations (Li2P and Na2P) lead to the softening of black phosphorous, whereas magnesiation shows a hardening phenomenon. In addition, the diffusion of Li/Na/Mg in black phosphorus during the intercalation process is an easy process along one-dimensional channels in black phosphorus with marginal energy barriers. The diffusion of Li has a lower energy barrier in black phosphorus than in graphite.

Anisotropic Effective Mass, Optical Property, and Enhanced Band Gap in BN/Phosphorene/BN Heterostructures.

Phosphorene is receiving great research interests because of its peculiar physical properties. Nonetheless, the phosphorus has a trouble of degradation due to oxidation. Hereby, we propose that the electrical and optical anisotropic properties can be preserved by encapsulating into hexagonal boron nitride (h-BN). We found that the h-BN contributed to enhancing the band gap of the phosphorene layer. Comparing the band gap of the pristine phosphorene layer, the band gap of the phosphorene/BN(1ML) system was enhanced by 0.15 eV. It was further enhanced by 0.31 eV in the BN(1ML)/phosphorene/BN(1ML) trilayer structure. However, the band gap was not further enhanced when we increased the thickness of the h-BN layers even up to 4 MLs. Interestingly, the anisotropic effective mass and optical property were still preserved in BN/phosphorene/BN heterostructures. Overall, we predict that the capping of phosphorene by the h-BN layers can be an excellent solution to protect the intrinsic properties of the phosphorene.

A phosphorene-graphene hybrid material as a high-capacity anode for sodium-ion batteries.

Sodium-ion batteries have recently attracted significant attention as an alternative to lithium-ion batteries because sodium sources do not present the geopolitical issues that lithium sources might. Although recent reports on cathode materials for sodium-ion batteries have demonstrated performances comparable to their lithium-ion counterparts, the major scientific challenge for a competitive sodium-ion battery technology is to develop viable anode materials. Here we show that a hybrid material made out of a few phosphorene layers sandwiched between graphene layers shows a specific capacity of 2,440 mA h g(-1) (calculated using the mass of phosphorus only) at a current density of 0.05 A g(-1) and an 83% capacity retention after 100 cycles while operating between 0 and 1.5 V. Using in situ transmission electron microscopy and ex situ X-ray diffraction techniques, we explain the large capacity of our anode through a dual mechanism of intercalation of sodium ions along the x axis of the phosphorene layers followed by the formation of a Na3P alloy. The presence of graphene layers in the hybrid material works as a mechanical backbone and an electrical highway, ensuring that a suitable elastic buffer space accommodates the anisotropic expansion of phosphorene layers along the y and z axial directions for stable cycling operation.

2D MATERIALS. Observation of tunable band gap and anisotropic Dirac semimetal state in black phosphorus.

Black phosphorus consists of stacked layers of phosphorene, a two-dimensional semiconductor with promising device characteristics. We report the realization of a widely tunable band gap in few-layer black phosphorus doped with potassium using an in situ surface doping technique. Through band structure measurements and calculations, we demonstrate that a vertical electric field from dopants modulates the band gap, owing to the giant Stark effect, and tunes the material from a moderate-gap semiconductor to a band-inverted semimetal. At the critical field of this band inversion, the material becomes a Dirac semimetal with anisotropic dispersion, linear in armchair and quadratic in zigzag directions. The tunable band structure of black phosphorus may allow great flexibility in design and optimization of electronic and optoelectronic devices.

Exfoliated layers of black phosphorus as saturable absorber for ultrafast solid-state laser.

High-quality black phosphorus (BP) saturable absorber mirror (SAM) was successfully fabricated with few-layered BP (phosphorene). By employing the prepared phosphorene SAM, we have demonstrated ultrafast pulse generation from a BP mode-locked bulk laser for the first time to our best knowledge. Pulses as short as 6.1ps with an average power of 460mW were obtained at the central wavelength of 1064.1nm. Considering the direct and flexible band gap for different layers of phosphorene, this work may provide a possible method for fabricating BP SAM to achieve ultrafast solid-state lasers in IR and mid-IR wavelength region.

Electronic structure and magnetic properties of zigzag blue phosphorene nanoribbons

We investigated the electronic structure and magnetism of zigzag blue phosphorene nanoribbons (ZBPNRs) using first principles density functional theory calculations by changing the widths of ZBPNRs from 1.5 to 5 nm. In addition, the effect of H and O passivation was explored as well. The ZBPNRs displayed intra-edge antiferromagnetic ground state with a semiconducting band gap of ∼0.35 eV; and this was insensitive to the edge structure relaxation effect. However, the edge magnetism of ZBPNRs disappeared with H-passivation. Moreover, the band gap of H-passivated ZBPNRs was greatly enhanced because the calculated band gap was ∼1.77 eV, and this was almost the same as that of two-dimensional blue phosphorene layer. For O-passivated ZBPNRs, we also found an intra-edge antiferromagnetic state. Besides, both unpassivated and O-passivated ZBPNRs preserved almost the same band gap. We predict that the electronic band structure and magnetic properties can be controlled by means of passivation. Moreover, the edge magnetism can be also modulated by the strain. Nonetheless, the intrinsic physical properties are size independent. This feature can be an advantage for device applications because it may not be necessary to precisely control the width of the nanoribbon.

Anisotropic bias dependent transport property of defective phosphorene layer.

Phosphorene is receiving great research interests because of its peculiar physical properties. Nonetheless, no systematic studies on the transport properties modified due to defects have been performed. Here, we present the electronic band structure, defect formation energy and bias dependent transport property of various defective systems. We found that the defect formation energy is much less than that in graphene. The defect configuration strongly affects the electronic structure. The band gap vanishes in single vacancy layers, but the band gap reappears in divacancy layers. Interestingly, a single vacancy defect behaves like a p-type impurity for transport property. Unlike the common belief, we observe that the vacancy defect can contribute to greatly increasing the current. Along the zigzag direction, the current in the most stable single vacancy structure was significantly increased as compared with that found in the pristine layer. In addition, the current along the armchair direction was always greater than along the zigzag direction and we observed a strong anisotropic current ratio of armchair to zigzag direction.

Optical tuning of exciton and trion emissions in monolayer phosphorene

Monolayer phosphorene provides a unique two-dimensional (2D) platform to investigate the fundamental dynamics of excitons and trions (charged excitons) in reduced dimensions. However, owing to its high instability, unambiguous identification of monolayer phosphorene has been elusive. Consequently, many important fundamental properties, such as exciton dynamics, remain underexplored. We report a rapid, noninvasive, and highly accurate approach based on optical interferometry to determine the layer number of phosphorene, and confirm the results with reliable photoluminescence measurements. Furthermore, we successfully probed the dynamics of excitons and trions in monolayer phosphorene by controlling the photo-carrier injection in a relatively low excitation power range. Based on our measured optical gap and the previously measured electronic energy gap, we determined the exciton binding energy to be ∼0.3 eV for the monolayer phosphorene on SiO2/Si substrate, which agrees well with theoretical predictions. A huge trion binding energy of ∼100 meV was first observed in monolayer phosphorene, which is around five times higher than that in transition metal dichalcogenide (TMD) monolayer semiconductor, such as MoS2. The carrier lifetime of exciton emission in monolayer phosphorene was measured to be ∼220 ps, which is comparable to those in other 2D TMD semiconductors. Our results open new avenues for exploring fundamental phenomena and novel optoelectronic applications using monolayer phosphorene. An optical scheme for determining the number of monolayers on two-dimensional materials has been developed. Research into two-dimensional materials is thriving, but developing a way to identify a single monolayer has proved challenging. Now, Jiong Yang and co-workers have used phase-shifting interferometry to deduce the number of phosphorene layers. They then performed power-dependent photoluminescence measurements to determine various excitonic properties of a monolayer on a silicon oxide/silicon substrate. They obtained an exciton binding energy of about 0.3 electron volts, which agrees well with theoretical predictions. The researchers measured a carrier lifetime of approximately 220 picoseconds, which is comparable to that of the transition-metal dichalcogenides, another class of two-dimensional semiconductors. They also measured a trion binding energy of about 100 milli-electron volts, which is around five times higher than that of transition-metal dichalcogenides.