Few-layer Black Phosphorus Research Articles

Abnormal behavior of potassium adsorbed phosphorene

First-principles calculation is carried out to study adsorption of potassium (K) on phosphorene, a single layer of black phosphorus (BP). Interesting adsorption distance dependent electronic properties were found for the K adsorption on phosphorene surface, which is different from that for the K adsorption on a few-layer black phosphorus. While the bandgap of few-layer BP decreases monotonically as K approaches its surface and a Dirac point emerges, that of phosphorene decreases first and then increases, remaining open at any separation between K and phosphorene. This abnormal behavior is a result of weaker Stark effect and charge localization in phosphorene.

Tight binding parametrization of few-layer black phosphorus from first-principles calculations

We employ a tight-binding parametrization based on the Slater Koster model in order to fit the band structures of single-layer, bilayer and bulk black phosphorus obtained from first-principles calculations. We find that our model, which includes 9 or 17 parameters depending on whether overlap is included or not, reproduces quite well the ab initio band structures over a wide energy range, especially the occupied bands. We also find that the Inclusion of overlap parameters improves the quality of the fit for the conduction bands. On the other hand, hopping and on-site energies are consistent throughout the different systems, which is an indication that our model is suitable for calculations on multilayer black phosphorus and more complex situations in which first-principles calculations become prohibitive, such as disordered systems and heterostructures with a large lattice mismatch. We also discuss the limitations of the model and how the fit procedure can be improved for a more accurate description of bands in the vicinity of the Fermi energy.

Germanium-doped Metallic Ohmic Contacts in Black Phosphorus Field-Effect Transistors with Ultra-low Contact Resistance

In this work, we demonstrate for the first time an ultra-low contact resistance few-layered black phosphorus (BP) transistor with metallic PGex contacts formed by rapid thermal annealing (RTA). The on-state current of the transistor can be significantly improved and the ION/IOFF ratio increases by almost 2 order. The hole mobility is enhanced by 25 times to 227 cm2V−1s−1. The contact resistance extracted by the transfer length method is 0.365 kΩ∙μm, which is the lowest value in black phosphorus transistors without degradation of ION/IOFF ratio. In addition, the I-V curve of the transistor with PGex contact is linear compared to that with Ti contact at 80 K, indicating that a metallic ohmic contact is successfully formed. Finally, X-ray photoelectron spectroscopy is used to characterize the PGex compound. A signal of P-Ge bond is first observed, further verifying the doping of Ge into BP and the formation of the PGex alloy.

Black-Phosphorus-Based Orientation-Induced Diodes.

Despite many decades of research of diodes, which are fundamental components of electronic and photoelectronic devices with p-n or Schottky junctions using bulk or 2D materials, stereotyped architectures and complex technological processing (doping and multiple material operations) have limited future development. Here, a novel rectification device, an orientation-induced diode, assembled using only few-layered black phosphorus (BP) is investigated. The key to its realization is to utilize the remarkable anisotropy of BP in low dimensions and change the charge-transport conditions abruptly along the different crystal orientations. Rectification ratios of 6.8, 22, and 115 can be achieved in cruciform BP, cross-stacked BP junctions, and BP junctions stacked with vertical orientations, respectively. The underlying physical processes and mechanisms can be explained using "orientation barrier" band theory. The theoretical results are experimentally confirmed using localized scanning photocurrent imaging. These orientation-induced optoelectronic devices open possibilities for 2D anisotropic materials with a new degree of freedom to improve modulation in diodes.

Single Pixel Black Phosphorus Photodetector for Near-Infrared Imaging.

Infrared imaging systems have wide range of military or civil applications and 2D nanomaterials have recently emerged as potential sensing materials that may outperform conventional ones such as HgCdTe, InGaAs, and InSb. As an example, 2D black phosphorus (BP) thin film has a thickness-dependent direct bandgap with low shot noise and noncryogenic operation for visible to mid-infrared photodetection. In this paper, the use of a single-pixel photodetector made with few-layer BP thin film for near-infrared imaging applications is demonstrated. The imaging is achieved by combining the photodetector with a digital micromirror device to encode and subsequently reconstruct the image based on compressive sensing algorithm. Stationary images of a near-infrared laser spot (λ = 830 nm) with up to 64 × 64 pixels are captured using this single-pixel BP camera with 2000 times of measurements, which is only half of the total number of pixels. The imaging platform demonstrated in this work circumvents the grand challenges of scalable BP material growth for photodetector array fabrication and shows the efficacy of utilizing the outstanding performance of BP photodetector for future high-speed infrared camera applications.

One-dimensional phosphorus chain and two-dimensional blue phosphorene grown on Au(111) by molecular-beam epitaxy

Single layer (SL) phosphorus (phosphorene) has drawn considerable research attention recently as a two-dimensional (2D) material for application promises. It is a semiconductor showing superior transport and optical properties. Few-layer or SL black phosphorus has been successfully isolated by exfoliation from bulk crystals and extensively studied thereof for its electronic and optical properties. Blue phosphorus (blueP), an allotrope of black phosphorus where atoms are arranged in a more flat atomic configuration, has been recently suggested by theory to exist in the SL form on some substrates. In this work, we report the formation of a blueP-like epilayer on Au(111) by molecular-beam epitaxy. In particular, we uncover by scanning tunneling microscopy (STM) one-dimensional (1D) atomic chains at low coverage, which develop into more compact islands or patches of $(\sqrt{3}\times\sqrt{3})R30^\circ$ structure with increasing coverage before blueP-like islands nucleate and grow. We also note an interesting growth characteristic where the $(\sqrt{3}\times\sqrt{3})R30^\circ$ surface at intermediate coverage tends to phase-separate into locally low-coverage 1D chain and high-coverage blueP-like structures, respectively. This experiment thus not only lends a support of the recently proposed half-layer by half-layer (HLBHL) growth mechanism but also reveals the kinetic details of blueP growth processes.

Graphene/phosphorene nano-heterojunction: facile synthesis, nonlinear optics, and ultrafast photonics applications with enhanced performance

Owing to its thickness-modulated direct energy band gap, relatively strong light–matter interaction, and unique nonlinear optical response at a long wavelength, few-layer black phosphorus, or phosphorene, becomes very attractive in ultrafast photonics applications. Herein, we synthesized a graphene/phosphorene nano-heterojunction using a liquid phase-stripping method. Tiny lattice distortions in graphene and phosphorene suggest the formation of a nano-heterojunction between graphene and phosphorene nanosheets. In addition, we systematically investigate their nonlinear optical responses at different wavelength regimes. Our experiments indicate that the combined advantages of ultrafast relaxation, broadband response in graphene, and the strong light–matter interaction in phosphorene can be combined together by nano-heterojunction. We have further fabricated two-dimensional (2D) nano-heterojunction based optical saturable absorbers and integrated them into an erbium-doped fiber laser to demonstrate the generation of a stable ultrashort pulse down to 148 fs. Our results indicate that a graphene/phosphorene nano-heterojunction can operate as a promising saturable absorber for ultrafast laser systems with ultrahigh pulse energy and ultranarrow pulse duration. We believe this work opens up a new approach to designing 2D heterointerfaces for applications in ultrafast photonics and other research. The fabrication of a 2D nano-heterojunction assembled from stacking different 2D materials, via this facile and scalable growth approach, paves the way for the formation and tuning of new 2D materials with desirable photonic properties and applications.

Efficiency Enhancement of Single‐Walled Carbon Nanotube‐Silicon Heterojunction Solar Cells Using Microwave‐Exfoliated Few‐Layer Black Phosphorus

AbstractCarbon nanotube‐silicon (CNT‐Si)‐based heterojunction solar cells (HJSCs) are a promising photovoltaic (PV) system. Herein, few‐layer black phosphorus (FL‐BP) sheets are produced in N‐methyl‐2‐pyrrolidone (NMP) using microwave‐assisted liquid‐phase exfoliation and introduced into the CNTs‐Si‐based HJSCs for the first time. The NMP‐based FL‐BP sheets remain stable after mixing with aqueous CNT dispersion for device fabrication. Due to their unique 2D structure and p‐type dominated conduction, the FL‐BP/NMP incorporated CNT‐Si devices show an impressive improvement in the power conversion efficiency from 7.52% (control CNT‐Si cell) to 9.37%. Our density‐functional theory calculation reveals that lowest unoccupied molecular orbital (LUMO) of FL‐BP is higher in energy than that of single‐walled CNT. Therefore, we observed a reduction in the orbitals localized on FL‐BP upon highest occupied molecular orbital to LUMO transition, which corresponds to an improved charge transport. This study opens a new avenue in utilizing 2D phosphorene nanosheets for next‐generation PVs.

Identification of Lattice Oxygen in Few-Layer Black Phosphorous Exfoliated in Ultrahigh Vacuum and Largely Improved Ambipolar Field-Effect Mobilities by Hydrogenation and Phosphorization.

Black phosphorus (BP) has recently attracted considerable attention due to its unique structure and fascinating optical and electronic properties as well as possible applications in photothermal agents. However, its main drawback is rapid degradation in ambient environments of H2O and O2, which has led to much research on the improvement of its stability. Unfortunately, this research has not shown great improvement in carrier mobilities. Here, we perform scanning tunneling microscopy observations of few-layer BP (FLBP) sheets exfoliated in ultrahigh vacuum and reveal, for the first time, the existence of lattice oxygen introduced during crystal growth. As a proof-of-concept application, hydrogenation is conducted to remove the lattice oxygen atoms followed by phosphorization, which repairs the phosphorous vacancies caused by mechanical exfoliation and hydrogenation. The resulting FLBP sheets show high ambipolar field-effect mobilities of 1374 cm2 V-1 s-1 for holes and 607 cm2 V-1 s-1 for electrons at 2 K. After storage in air for 3 days, the hole and electron mobilities only decrease to 1181 and 518 cm2 V-1 s-1, respectively, and no structural degradation is observed. This work suggests an effective means to improve both the mobility and stability of BP sheets rendering practical application of FLBP sheets possible.

Ambipolar quantum transport in few-layer black phosphorus

We have investigated the quantum transport properties of high-mobility electrons and holes in atomically thin black phosphorus ambipolar devices. The two-dimensional hole system exhibits unambiguously the quantum Hall effect in a magnetic field up to 30 T, while the electron system shows clearly developing Hall plateaus at integer Landau level filling factors accompanied by ${R}_{xx}$ oscillations, signaling the onset of the quantum Hall effect. By bringing the spin-resolved Landau levels of the electron system to a coincidence, we determine an electron spin susceptibility to be ${\ensuremath{\chi}}_{se}={m}^{*}{g}^{*}=1.1\ifmmode\pm\else\textpm\fi{}0.03$, which, combined with the electron mass ${m}^{*}=0.39\phantom{\rule{0.16em}{0ex}}{m}_{0}$, yields a Land\'e $g$ factor ${g}^{*}=2.8\ifmmode\pm\else\textpm\fi{}0.2$. The enhancement of spin susceptibility in the black phosphorus two-dimensional electron system is around 50% compared with band susceptibility, which agrees well with various two-dimensional charge-carrier systems with weak spin-orbit coupling, suggesting the important role played by the exchange interaction.

Charged defects in two-dimensional semiconductors of arbitrary thickness and geometry: Formulation and application to few-layer black phosphorus

Energy evaluation of charged defects is tremendously important in two-dimensional (2D) semiconductors for the industrialization of 2D electronic devices because of its close relation with the corresponding type of conductivity and its strength. Although the method to calculate the energy of charged defects in single-layer one-atom-thick systems of equilateral unit-cell geometry has recently been proposed, few-layer 2D semiconductors are more common in device applications. As it turns out, one may not apply the one-layer formalism to multilayer cases without jeopardizing accuracy. Here, we generalize the approach to 2D systems of arbitrary cell geometry and thickness and use few-layer black phosphorus to illustrate how defect properties, mainly group-VI substitutional impurities, are affected. Within the framework of density functional theory, we show that substitutional Te $(\mathrm{T}{\mathrm{e}}_{\mathrm{P}})$ is the best candidate for $n$-type doping, and as the thickness increases, the ionization energy is found to decrease monotonically from 0.67 eV (monolayer) to 0.47 eV (bilayer) and further to 0.33 eV (trilayer). Although these results show the ineffectiveness of the dielectric screening at the monolayer limit, they also show how it evolves with increasing thickness whereby setting a new direction for the design of 2D electronics. The proposed method here is generally suitable to all the 2D materials regardless of their thickness and geometry.

Highly Efficient and Air-Stable Infrared Photodetector Based on 2D Layered Graphene-Black Phosphorus Heterostructure.

The presence of a direct band gap and high carrier mobility in few-layer black phosphorus (BP) offers opportunities for using this material for infrared (IR) light detection. However, the poor air stability of BP and its large contact resistance with metals pose significant challenges to the fabrication of highly efficient IR photodetectors with long lifetimes. In this work, we demonstrate a graphene-BP heterostructure photodetector with ultrahigh responsivity and long-term stability at IR wavelengths. In our device architecture, the top layer of graphene functions not only as an encapsulation layer but also as a highly efficient transport layer. Under illumination, photoexcited electron-hole pairs generated in BP are separated and injected into graphene, significantly reducing the Schottky barrier between BP and the metal electrodes and leading to efficient photocurrent extraction. The graphene-BP heterostructure phototransistor exhibits a long-term photoresponse at near-infrared wavelength (1550 nm) with an ultrahigh photoresponsivity (up to 3.3 × 103 A W-1), a photoconductive gain (up to 1.13 × 109), and a rise time of about 4 ms. Considering the thickness-dependent band gap in BP, this material represents a powerful photodetection platform that is able to sustain high performance in the IR wavelength regime with potential applications in remote sensing, biological imaging, and environmental monitoring.

Midinfrared Electro-optic Modulation in Few-Layer Black Phosphorus.

Black phosphorus stands out from the family of two-dimensional materials as a semiconductor with a direct, layer-dependent bandgap spanning the visible to mid-infrared (mid-IR) spectral range. It is, therefore, a very promising material for various optoelectronic applications, particularly in the important mid-IR range. While mid-IR technology has been advancing rapidly, both photodetection and electro-optic modulation in the mid-IR rely on narrow-band compound semiconductors, which are difficult and expensive to integrate with the ubiquitous silicon photonics. For mid-IR photodetection, black phosphorus has already been proven to be a viable alternative. Here, we demonstrate electro-optic modulation of mid-IR absorption in few-layer black phosphorus. Our experimental and theoretical results find that, within the doping range obtainable in our samples, the quantum confined Franz-Keldysh effect is the dominant mechanism of electro-optic modulation. A spectroscopic study on samples with varying thicknesses reveals strong layer dependence in the interband transition between specific pairs of sub-bands. Our results show that black phosphorus is a very promising material to realizing efficient mid-IR modulators.

Phosphorene-directed self-assembly of asymmetric PS-b-PMMA block copolymer for perpendicularly-oriented sub-10 nm PS nanopore arrays

Few-layer black phosphorus, also known as phosphorene, is a new two-dimensional material which is of enormous interest for applications, mainly in electronics and optoelectronics. Herein, we for the first time employ phosphorene for directing the self-assembly of asymmetric polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymer (BCP) thin film to form the perpendicular orientation of sub-10 nm PS nanopore arrays in a hexagonal fashion normal to the interface. We experimentally demonstrate that none of the PS and PMMA blocks exhibit preferential affinity to the phosphorene-modified surface. Furthermore, the perpendicularly-oriented PS nanostructures almost stay unchanged with the variation of number of layers of few-layer phosphorene nanoflakes between 15–30 layers. Differing from the neutral polymer brushes which are widely used for chemical modification of the silicon substrate, phosphorene provides a novel physical way to control the interfacial interactions between the asymmetric PS-b-PMMA BCP thin film and the silicon substrate. Based on our results, it is possible to build a new scheme for producing sub-10 nm PS nanopore arrays oriented perpendicularly to the few-layer phosphorene nanoflakes. Furthermore, the nanostructural microdomains could serve as a promising nanolithography template for surface patterning of phosphorene nanoflakes.

Highly efficient and continuous production of few-layer black phosphorus nanosheets and quantum dots via acoustic-microfluidic process

Few-layer black phosphorus (BP) with tunable band gap and excellent electronic properties is an emerging two dimensional semiconductor that has been demonstrated to be useful in many applications. Here we introduce an acoustic-microfluidic (AM) process for exfoliation of BP powder to produce few-layer BP flakes and BP quantum dots (BPQDs) in a continuous-flow process. The AM process yielded a 45wt% exfoliation efficiency in 6min, and produced few-layer BP flakes of stripe shape with a lateral size of 434±135nm and a thickness of 2.5±1.2nm, corresponding to 2–4 layers of phosphorene, at a production rate of 9.8mghr−1. In contrast, the conventional batch process yielded an exfoliation efficiency of only 14wt% even after 6 hrs, and produced larger and thicker BP flakes. Furthermore, prolonging the AM process to additional 12min resulted in efficient fragmentation of the flakes into a few nanometer BPQDs (diameter 2.6±1.0, thickness 1.7±0.6nm). The efficiency in the exfoliation and subsequent fragmentation can be attributed to the cavity activities maximized by flow rate. The AM-exfoliated BP nanosheets and BPQDs is found to be stable in 8months aging as long as their exposure to air and water is avoided.

Strain-Modulated Bandgap and Piezo-Resistive Effect in Black Phosphorus Field-Effect Transistors.

Energy bandgap largely determines the optical and electronic properties of a semiconductor. Variable bandgap therefore makes versatile functionality possible in a single material. In layered material black phosphorus, the bandgap can be modulated by the number of layers; as a result, few-layer black phosphorus has discrete bandgap values that are relevant for optoelectronic applications in the spectral range from red, in monolayer, to mid-infrared in the bulk limit. Here, we further demonstrate continuous bandgap modulation by mechanical strain applied through flexible substrates. The strain-modulated bandgap significantly alters the density of thermally activated carriers; we for the first time observe a large piezo-resistive effect in black phosphorus field-effect transistors (FETs) at room temperature. The effect opens up opportunities for future development of electromechanical transducers based on black phosphorus, and we demonstrate an ultrasensitive strain gauge constructed from black phosphorus thin crystals.

Black Phosphorus Nanoflakes/Polyaniline Hybrid Material for High-Performance Pseudocapacitors

Electrochemical supercapacitors based on conducting polymers are promising energy storage devices which can combine the merits of both rechargeable batteries and conventional electrostatic capacitors. Herein, we demonstrate that the novel hybrid electrode material made of few-layered black phosphorus (BP) and polyaniline (PANI) can outperform the constructing components. BP/PANI nanocomposite demonstrates high specific capacitance of 354 F g–1 at a current density of 0.3 A g–1. The 2D morphology of BP nanosheets provides large-surface-area support for nucleation of PANI, thus offering more ion-accessible sites to the active material.

Functionalized few-layer black phosphorus with super-wettability towards enhanced reaction kinetics for rechargeable batteries

Few-layer black phosphorus (BP) is a promising anode material for sodium ion batteries (SIBs) due to its high theoretical capacity and favorable layered structure. However, practical implementation is hindered by sluggish reaction kinetics and large volume change during de/sodiation process. Especially, combining BP with large portion of low-capacity carbonaceous materials is a common strategy to improve the Na storage properties, but leading to reduced specific capacity based on the overall mass of the whole electrode. To address these challenges, nanoscale surface engineering of few-layer BP is herein performed by homogeneously depositing horizontally aligned Poly(3, 4-ethylenedioxythiophene) (PEDOT) nanofibers on specially surface-modified BP nanosheets. Such material design could achieve simultaneously: (1) enhanced charge transfer kinetics and (2) super surface wettability with electrolyte. Benefiting from the unique functionalization, the reaction kinetics are greatly enhanced accordingly for both sodium and lithium storage. Our strategy sheds light on designing advanced electrodes for high-performance rechargeable batteries and other energy storage/conversion devices.

Microscopic mechanism of the tunable band gap in potassium-doped few-layer black phosphorus

Tuning band gaps in two-dimensional (2D) materials is of great interest for the fundamental and practical aspects of contemporary material sciences. Recently, black phosphorus (BP) consisting of stacked layers of phosphorene was experimentally observed to show a widely tunable band gap by means of the deposition of potassium (K) atoms on the surface, thereby allowing great flexibility in the design and optimization of electronic and optoelectronic devices. Here, based on density-functional theory calculations, we demonstrates that the donated electrons from K dopants are mostly localized in the topmost BP layer and this surface charging efficiently screens the K ion potential. It is found that, as the K doping increases, the extreme surface charging and its screening of K atoms shift the conduction bands down in energy, i.e., towards a higher binding energy, because they have more charge near the surface, while it has little influence on the valence bands having more charge in the deeper layers. This result provides a different explanation for the observed tunable band gap compared to the previously proposed giant Stark effect where a vertical electric field from the positively ionized K overlayer to the negatively charged BP layers shifts the conduction band minimum ${\mathrm{\ensuremath{\Gamma}}}_{1\mathrm{c}}$ (valence band minimum ${\mathrm{\ensuremath{\Gamma}}}_{8\mathrm{v}}$) downwards (upwards). The present prediction of ${\mathrm{\ensuremath{\Gamma}}}_{1\mathrm{c}}$ and ${\mathrm{\ensuremath{\Gamma}}}_{8\mathrm{v}}$ as a function of the K doping reproduces well the widely tunable band gap, anisotropic Dirac semimetal state, and band-inverted semimetal state, as observed in an angle-resolved photoemission spectroscopy experiment. Our findings shed new light on a route for tunable band gap engineering of 2D materials through the surface doping of alkali metals.

Passively mode-locked 134 μm bulk laser based on few-layer black phosphorus saturable absorber

By using few-layer black phosphorus (BP) as saturable absorber, an efficient mode-locked Nd:GdVO4 bulk laser operating at 1.34 μm was realized. An average output power of 350 mW was achieved with a slope efficiency of 15%. The corresponding mode-locking pulse repetition rate, pulse duration and pulse energy were 58.14 MHz, 9.24 ps and 3.0 nJ, respectively. To the best of our knowledge, the pulse width is the shortest among the mode-locked 1.34 μm neodymium lasers ever obtained with other two-dimensional materials saturable absorber. The results clearly indicate the few-layered BP is a kind of promising saturable absorber for ultrafast 1.34 μm lasers.