Few-layer Black Phosphorus Research Articles

Infrared fingerprints of few-layer black phosphorus

Black phosphorus is an infrared layered material. Its bandgap complements other widely studied two-dimensional materials: zero-gap graphene and visible/near-infrared gap transition metal dichalcogenides. Although highly desirable, a comprehensive infrared characterization is still lacking. Here we report a systematic infrared study of mechanically exfoliated few-layer black phosphorus, with thickness ranging from 2 to 15 layers and photon energy spanning from 0.25 to 1.36 eV. Each few-layer black phosphorus exhibits a thickness-dependent unique infrared spectrum with a series of absorption resonances, which reveals the underlying electronic structure evolution and serves as its infrared fingerprints. Surprisingly, unexpected absorption features, which are associated with the forbidden optical transitions, have been observed. Furthermore, we unambiguously demonstrate that controllable uniaxial strain can be used as a convenient and effective approach to tune the electronic structure of few-layer black phosphorus. Our study paves the way for black phosphorus applications in infrared photonics and optoelectronics.

Current progress in black phosphorus materials and their applications in electrochemical energy storage.

Recently, a new two-dimensional material, single- or few-layered black phosphorus (BP), has attracted considerable attention for applications in electronics, optoelectronics, and batteries due to its unique properties, including large specific surface area, anisotropy, and tunable and direct band gaps. In particular, contributions to electrochemical energy storage devices, such as lithium and sodium ion batteries and supercapacitors, have emerged. However, critical issues remain to be explored before scaled-up commercial production of BP, such as preparation, stability, and performance. Herein, we present the first review of recent progress in BP-based electrochemical energy storage device. The preparation and electrochemical properties of black phosphorus, recent advances, potential challenges, and relevant perspectives in electrochemical energy storage, and the potential of BP are discussed in this work.

Generation of Mode-Locked Ytterbium Doped Fiber Ring Laser Using Few-Layer Black Phosphorus as a Saturable Absorber

We demonstrate the generation of mode-locked pulses from a double-clad ytterbium-doped fiber laser (YDFL) employing a saturable absorber (SA) made of a few layers of black phosphorus (BP). The BP SA was prepared by mechanically exfoliating BP crystal and spreading the acquired BP flakes on a piece of scotch tape. The tape was then sandwiched between two ferrules and incorporated in a YDFL cavity to achieve a stable mode-locked operation at 1085.58 nm with a repetition rate of 13.5 MHz. A maximum pulse energy of 5.93 nJ was obtained at pump power of 1322 mW with the output power of 80 mW. Our study may well be the first demonstration of the BP-based mode-locked fiber laser that should shed some new insights into two-dimensional layer materials related photonics.

Anisotropic atomic-structure related anomalous Hall resistance in few-layer black phosphorus

Specific anisotropic-atomic-structure of atom-thin black phosphorus causes the anomalous magnetic-field dependence of the Hall resistance, which opens doors to novel quantum phenomena and innovative two-dimensional atom-thin devices.

Evolution of hydrogen by few-layered black phosphorus under visible illumination

Combined theoretical as well as experimental results provide evidence of hydrogen (H2) evolution from aqueous solution by using few layered black phosphorus (nanosheets and nanoparticles) under visible light illumination.

Compressed few-layer black phosphorus nanosheets from semiconducting to metallic transition with the highest symmetry

The high-pressure response of few-layer black phosphorus (BP) nanosheets remains elusive, despite the special interest in it particularly after the achievement of an exotic few-layer BP based field effect transistor. Here, we identified a pressure-induced reversible phase transition on few-layer BP nanosheets by performing in situ ADXRD and Raman spectroscopy with the assistance of DAC apparatus. The few-layer BP nanosheets transformed from orthorhombic semiconductors to simple cubic metal with increasing pressure, which is well interpreted using the pressure-induced inverse Peierls distortion. The obtained simple cubic BP nanosheets exhibited an enhanced isothermal bulk modulus of 147.0(2) GPa, and negative Grüneisen parameters that were attributed to the pressure-driven softening of phonon energies. Note that the simple cubic BP nanosheets adopted the highest symmetry which is in stark contrast to the general phase transformation under high pressure. First-principles calculations indicated that the metallic BP was significantly related to the band overlapped metallization, resulting from the traversing of density of states across the Fermi level at high pressure. Such findings paved a potential pathway to design targeted BP nanostructures with functional properties at extremes, and opened up possibilities for conceptually new devices.

Few-layer selenium-doped black phosphorus: synthesis, nonlinear optical properties and ultrafast photonics applications

The synthesized FL Se-doped compound shows enhanced optical saturable absorption and high electrical characterizations, which can be developed as an excellent candidate for photoelectric devices.

Band-edge engineering via molecule intercalation: a new strategy to improve stability of few-layer black phosphorus.

The poor environmental stability of black phosphorous (BP) seriously limits its practical applications in (opto)electronics. Other than capping protective layers on its surface, herein we propose a new strategy to improve BP's ambient stability by engineering the interlayer interactions. Our first-principles calculations demonstrate that enlarging the interlayer spacing can effectively shift the conduction band minimum down to suppress the generation of superoxide and the enlargement can be achieved by intercalating small molecules like H2 and He into BP. Moreover, the molecule intercalated BP maintains high hole mobility, which makes it a better two-dimensional semiconductor for practical applications.

Large edge magnetism in oxidized few-layer black phosphorus nanomeshes

The formation and control of a room-temperature magnetic order in two-dimensional (2D) materials is a challenging quest for the advent of innovative magnetic- and spintronic-based technologies. To date, edge magnetism in 2D materials has been experimentally observed in hydrogen (H)-terminated graphene nanoribbons (GNRs) and graphene nanomeshes (GNMs), but the measured magnetization remains far too small to allow envisioning practical applications. Herein, we report experimental evidences of large room-temperature edge ferromagnetism (FM) obtained from oxygen (O)-terminated zigzag pore edges of few-layer black phosphorus (P) nanomeshes (BPNMs). The magnetization values per unit area are ~100 times larger than those reported for H-terminated GNMs, while the magnetism is absent for H-terminated BPNMs. The magnetization measurements and the first-principles simulations suggest that the origin of such a magnetic order could stem from ferromagnetic spin coupling between edge P with O atoms, resulting in a strong spin localization at the edge valence band, and from uniform oxidation of full pore edges over a large area and interlayer spin interaction. Our findings pave the way for realizing high-efficiency 2D flexible magnetic and spintronic devices without the use of rare magnetic elements.

Achieving Ultrahigh Carrier Mobility in Two-Dimensional Hole Gas of Black Phosphorus.

We demonstrate that a field-effect transistor (FET) made of few-layer black phosphorus (BP) encapsulated in hexagonal boron nitride (h-BN) in vacuum exhibits a room-temperature hole mobility of 5200 cm2/(Vs), being limited just by the phonon scattering. At cryogenic temperatures, the FET mobility increases up to 45 000 cm2/(Vs), which is five times higher compared to the mobility obtained in earlier reports. The unprecedentedly clean h-BN-BP-h-BN heterostructure exhibits Shubnikov-de Haas oscillations and a quantum Hall effect with Landau level (LL) filling factors down to v = 2 in conventional laboratory magnetic fields. Moreover, carrier density independent effective mass of m* = 0.26 m0 is measured, and a Landé g-factor of g = 2.47 is reported. Furthermore, an indication for a distinct hole transport behavior with up- and down-spin orientations is found.

Defining the role of humidity in the ambient degradation of few-layer black phosphorus

Few-layer black phosphorus (BP) is an emerging material of interest for applications in electronics. However, lack of ambient stability is hampering its incorporation in practical devices as it demands for an inert operating environment. Here, we study the individual effects of key environmental factors, such as temperature, light and humidity on the deterioration of BP. It is shown that humidity on its own does not cause material degradation. In fact, few-layer BP is employed as a recoverable humidity sensor. This study eliminates humidity as an active parameter in BP degradation. Hence, by simply isolating BP from light, its lifetime can be prolonged even in the presence of O2. As such, this study opens the pathway for devising new strategies for the practical implementation of BP.

The Role of Air Adsorption in Inverted Ultrathin Black Phosphorus Field-Effect Transistors.

Few-layer black phosphorus (BP) attracts much attention owing to its high mobility and thickness-tunable band gap; however, compared with the commonly studied transition metal dichalcogenides (TMDCs), BP has the unfavorable property of degrading in ambient conditions. Here, we propose an inverted dual gates structure of ultrathin BP FET to research the air adsorption on BP. In fabrication process of back-gate BP FET, BP was transferred directly onto a wafer covered with electrodes. Thus, we can exclude the BP degradation during the process of electrodes fabrication, such as electron beam lithography (EBL) and thermal evaporation process. Furthermore, without any electrode covering BP, BP could be in full contact with the air; then the accurate effect of the air adsorption on BP can be researched in detail. The results clearly show that annealing can remove the p-doping resulted from the metastable oxygen adsorbed on the surface of BP, but the adsorption can be restored in a few hours exposure. In addition, both back and top gate inverted BP FETs exhibit a favorable performance. Therefore, this inverted structure is also an optional structure to reduce the influence of the instability of BP devices.

Stable high-power saturable absorber based on polymer-black-phosphorus films

Black phosphorus (BP), a rising two-dimensional material with a layer-number-dependent direct bandgap of 0.3–1.5 eV, is very interesting for optoelectronics applications from near- to mid-infrared wavebands. In the atmosphere, few-layer BP tends to be oxidized or degenerated during interacting with lasers. Here, we fabricate few-layer BP nanosheets based on a liquid exfoliation method using N-methylpyrrolidone as the dispersion liquid. By incorporating BP nanosheets with polymers (polyvinyl alcohol or high-melting-point polyimide), two flexible filmy BP saturable absorbers are fabricated to realize passive mode locking in erbium-doped fiber lasers. The polymer-BP saturable absorber, especially the polyimide-BP saturable absorber, can prevent the oxidation or water-induced etching under high-power laser illuminations, providing a promising candidate for Q-switchers, mode lockers, and light modulators.

Black phosphorus-based one-dimensional photonic crystals and microcavities.

The latest achievements in the fabrication of thin layers of black phosphorus (BP), toward the technological breakthrough of a phosphorene atomically thin layer, are paving the way for their use in electronics, optics, and optoelectronics. In this work, we have simulated the optical properties of one-dimensional photonic structures, i.e., photonic crystals and microcavities, in which few-layer BP is one of the components. The insertion of the 5-nm black phosphorous layers leads to a photonic band gap in the photonic crystals and a cavity mode in the microcavity that is interesting for light manipulation and emission enhancement.

Vector soliton fiber laser passively mode locked by few layer black phosphorus-based optical saturable absorber.

We report on the optical saturable absorption of few-layer black phosphorus nanoflakes and demonstrate its application for the generation of vector solitons in an erbium-doped fiber laser. By incorporating the black phosphorus nanoflakes-based saturable absorber (SA) into an all-fiber erbium-doped fiber laser cavity, we are able to obtain passive mode-locking operation with soliton pulses down to ~670 fs. The properties and dynamics of the as-generated vector solitons are experimentally investigated. Our results show that BP nanoflakes could be developed as an effective SA for ultrashort pulse fiber lasers, particularly for the generation of vector soliton pulses in fiber lasers.

Resonantly Increased Optical Frequency Conversion in Atomically Thin Black Phosphorus.

Optical frequency conversion via the nonlinear effect of third harmonic generation is shown to be resonantly enhanced in few-layer black phosphorus. This feature is believed to be a consequence of exciton-related resonance, as the enhancement is strongly correlated with the observation of exciton-recombination photoluminescence. Few-layer thicknesses are obtained both via mechanical exfoliation and laser thinning.

Inverse Funnel Effect of Excitons in Strained Black Phosphorus

We study the effects of strain on the properties and dynamics of Wannier excitons in monolayer (phosphorene) and few-layer black phosphorus (BP), a promising two-dimensional material for optoelectronic applications due to its high mobility, mechanical strength and strain-tuneable direct band gap. We compare the results to the case of molybdenum disulphide (MoS$_2$) monolayers. We find that the so-called funnel effect, i.e. the possibility of controlling exciton motion by means of inhomogeneous strains, is much stronger in few-layer BP than in MoS$_2$ monolayers and, crucially, is of opposite sign. Instead of excitons accumulating isotropically around regions of high tensile strain like in MoS$_2$, excitons in BP are pushed away from said regions. This \emph{inverse} funnel effect is moreover highly anisotropic, with much larger funnel distances along the armchair crystallographic direction, leading to a directional focusing of exciton flow. A strong inverse funnel effect could enable simpler designs of funnel solar cells, and offer new possibilities for the manipulation and harvesting of light.

Charge Trap Memory Based on Few-Layer Black Phosphorus and High-K Materials

Due to the unique properties of the two dimensional material, it has great potential for future information technology devices. Based on field-effect transistors with large hysteresis, consisting of a few-layer black phosphorus channel and a three dimensional (3D) Al2O3/HfO2/Al2O3, we successfully made the nonvolatile charge-trap memory devices. Because of the extraordinary trapping ability of the high-k HfO2, an unprecedented memory window exceeding 12 V is obtained. The device shows a high endurance of over 120 cycles and a stable retention of ∼30% charge loss after 10 years, even lower than the reported MoS2 flash memory. The high program/erase current ratio, large memory window, stable retention and high on/off current ratio, provide a promising route towards flexible and transparent memory devices utilizing atomically thin two-dimensional materials. The combination of 2D materials with traditional high-k charge-trap gate stacks opens up an exciting field of nonvolatile memory devices[1]. References (1) Qi Feng, Faguang Yan, Wengang Luo and Kaiyou Wang, Nanoscale, 8(2016)2686.

In situ thickness control of black phosphorus field-effect transistors via ozone treatment

A simple and reproducible method to control the thickness of black phosphorus flakes in real time using a UV/ozone treatment is demonstrated. Back-gated black phosphorus field-effect transistors (FETs) were fabricated using thick black phosphorus flakes obtained by thinning of black phosphorus, as oxygen radicals generated by UV irradiation formed phosphorus oxides on the surface. In order to monitor the thickness effect on the electrical properties, the fabricated FETs were loaded in the UV/ozone chamber, where both the optical (micro-Raman spectroscopy and optical microscopy) and electrical properties (current–voltage characteristics) were monitored in situ. We observed an intensity decrease of the Raman modes of black phosphorus while the field-effect mobility and on/off ratio increased by 48% and 6,800%, respectively. The instability in ambient air limits the investigation and implementation of ultra-thin black phosphorus. However, the method reported in this study allowed us to start with thick black phosphorous flakes, providing a reliable approach for optimizing the electrical performance of black phosphorus-based electronic devices. We believe that these results can motivate further studies using mono- and few-layer black phosphorus.

Nanostructured Aptamer-Functionalized Black Phosphorus Sensing Platform for Label-Free Detection of Myoglobin, a Cardiovascular Disease Biomarker.

We report the electrochemical detection of the redox active cardiac biomarker myoglobin (Mb) using aptamer-functionalized black phosphorus nanostructured electrodes by measuring direct electron transfer. The as-synthesized few-layer black phosphorus nanosheets have been functionalized with poly-l-lysine (PLL) to facilitate binding with generated anti-Mb DNA aptamers on nanostructured electrodes. This aptasensor platform has a record-low detection limit (∼0.524 pg mL(-1)) and sensitivity (36 μA pg(-1) mL cm(-2)) toward Mb with a dynamic response range from 1 pg mL(-1) to 16 μg mL(-1) for Mb in serum samples. This strategy opens up avenues to bedside technologies for multiplexed diagnosis of cardiovascular diseases in complex human samples.