Few-layer Black Phosphorus Research Articles

Passively Q-Switched Yb-Doped All-Fiber Laser With a Black Phosphorus Saturable Absorber

We report two kinds of Q-switched Yb-doped fiber lasers based on a black phosphorus saturable absorber (BP-SA). The BP-SAs are prepared by two different methods, one of which is the mechanical exfoliation method and the other is the liquid-phase exfoliation method. The BP-SAs are inserted into the all-fiber Yb-doped oscillation cavity in different forms. We have experimentally shown that the passively Q-switched pulse trains could be obtained by the two methods. First, we achieve the Q-switched pulse in 1029.63 nm by using a few-layer black phosphorus sheet. The fiber laser was capable of generating pulses with a maximum average output power of 13.12 mW and a repetition rate of 79.46 kHz, corresponding to the maximum single-pulse energy of 165.11 nJ and the shortest single-pulse width of 1.55 μs. In addition, we obtain narrower pulsewidth by dropping the black phosphorus solution onto the tapered fiber. The maximum single pulse energy of 114.72 nJ and the minimum pulsewidth of 1.09 μs were obtained. The repetition rate ranges from 49.13 to 101.3 kHz.

Controlled p-doping of black phosphorus by integration of MoS2 nanoparticles

Black phosphorus (BP), a new family of two dimensional (2D) layered materials, is an attractive material for future electronic, photonic and chemical sensing devices, thanks to its high carrier density and a direct bandgap of 0.3–2.0 eV, depending on the number of layers. Controllability over the properties of BP by electrical or chemical modulations is one of the critical requirements for future various device applications. Herein, we report a new doping method of BP by integration of density-controlled monolayer MoS2 nanoparticles (NPs). MoS2 NPs with different density were synthesized by chemical vapor deposition (CVD) and transferred onto a few-layer BP channel, which induced a p-doping effect. Scanning electron microscopy (SEM) confirmed the size and distribution of MoS2 NPs with different density. Raman and X-ray photoelectron spectroscopy (XPS) were measured to confirm the oxidation on the edge of MoS2 NPs and a doping effect of MoS2 NPs on a BP channel. The doping mechanism was explained by a charge transfer by work function differences between BP and MoS2 NPs, which was confirmed by Kelvin probe force microscopy (KPFM) and electrical measurements. The hole concentration of BP was controlled with different densities of MoS2 NPs in a range of 1012–1013 cm−2.

Black Phosphorus Synthesis Path Strongly Influences Its Delamination, Chemical Properties and Electrochemical Performance

We show here that synthetic approaches to layered black phosphorus (BP), namely, high-pressure conversion of red phosphorus (RP) and vapor growth of BP from RP in the presence of Sn/SnI4, lead to dramatically different crystallinity of BP which in turn strongly influences its exfoliation, chemical and electrochemical properties. In particular, we demonstrate that black phosphorus (BP) shear exfoliation in aqueous surfactant media can be used to obtain well-defined and few-layer BP nanosheets and that this depends on the crystallinity of BP. The process can proceed without the need to use glovebox or purging solutions. BP consisting of large well-developed crystals obtained by vapor growth methods and containing trace amounts of Sn is easily exfoliated. On other hand, highly pure nanocrystalline BP obtained by the high-pressure method could not be extensively exfoliated by shear mixing. Starting material BP crystallinity furthermore influences its counterpart shear exfoliated BP surface chemistry and elect...

Ultrafast Laser-Shock-Induced Confined Metaphase Transformation for Direct Writing of Black Phosphorus Thin Films.

Few-layer black phosphorus (BP) has emerged as one of the most promising candidates for post-silicon electronic materials due to its outstanding electrical and optical properties. However, lack of large-scale BP thin films is still a major roadblock to further applications. The most widely used methods for obtaining BP thin films are mechanical exfoliation and liquid exfoliation. Herein, a method of directly synthesizing continuous BP thin films with the capability of patterning arbitrary shapes by employing ultrafast laser writing with confinement is reported. The physical mechanism of confined laser metaphase transformation is understood by molecular dynamics simulation. Ultrafast laser ablation of BP layer under confinement can induce transient nonequilibrium high-temperature and high-pressure conditions for a few picoseconds. Under optimized laser intensity, this process induces a metaphase transformation to form a crystalline BP thin film on the substrate. Raman spectroscopy, atomic force microscopy, and transmission electron microscopy techniques are utilized to characterize the morphology of the resulting BP thin films. Field-effect transistors are fabricated on the BP films to study their electrical properties. This unique approach offers a general methodology to mass produce large-scale patterned BP films with a one-step manufacturing process that has the potential to be applied to other 2D materials.

Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries

The liquid-phase exfoliation (LPE) of black phosphorus (BP) is a strategic route for the large-scale production of phosphorene and few-layer BP (FL-BP) flakes. The exploitation of this exfoliated material in cutting-edge technologies, e.g., in flexible electronics and energy storage, is however limited by the fact that the LPE of BP is usually carried out at a high boiling point and in toxic solvents. In fact, the solvent residual is detrimental to device performance in real applications; thus, complete solvent removal is critical. Here, we tackle these issues by exfoliating BP in different low boiling-point solvents. Among these solvents, we find that acetone also provides a high concentration of exfoliated BP, leading to the production of FL-BP flakes with an average lateral size and thickness of c.a. 30 and 7 nm, respectively. The use of acetone to produce less defective few-layer BP flakes (FL-BPacetone) from bulk crystals is a straightforward process which enables the rapid preparation of homogeneous thin films thanks to the fast solvent evaporation. The ratio of edge to bulk atoms for the BP flakes here produced, combined with the use of low-boiling-point solvents for the exfoliation process suggests that these thin films are promising anodes for lithium-ion batteries. To this end, we tested Li-ion half cells with FL-BPacetone anodes achieving a reversible specific capacity of 480 mAh/g at a current density of 100 mA/g, over 100 charge/discharge cycles. Moreover, a reversible specific capacity of 345 mAh/g is achieved for the FL-BPacetone-based anode at a high current density (i.e., 1 A/g). These findings indicate that the FL-BPacetone-based battery is promising with regards to the design of fast charge/discharge devices. Overall, the presented process is a step forward toward the fabrication of phosphorene-based devices.

Omnipotent phosphorene: a next-generation, two-dimensional nanoplatform for multidisciplinary biomedical applications.

Phosphorene, also known as single- or few-layer black phosphorus (FLBP), is a new member of the two-dimensional (2D) material family and has attracted significant attention in recent years for applications in optoelectronics, energy storage and biomedicine due to its unique physicochemical properties and excellent biocompatibility. FLBP is regarded as a potential biological imaging agent for cancer diagnosis due to its intrinsic fluorescence (FL) and photoacoustic (PA) properties and negligible cytotoxicity. FLBP-based photothermal and photodynamic therapies have emerged with excellent anti-tumour therapeutic efficacies due to their unique physical properties, such as near-infrared (NIR) optical absorbance, large extinction coefficients, biodegradability and reactive oxygen species (ROS) or heat generation upon light irradiation. Furthermore, FLBP is a promising drug delivery platform because of its high drug-loading capacity due to its puckered layer structure with an ultralarge surface area, and FLBP is size-controllable with facile surface chemical modification. Because of the marked advantages of FLBP nanomaterials in biomedical applications, an overview of the latest progress and paradigms of FLBP-based nanoplatforms for multidisciplinary biomedical applications is presented in this tutorial review.

Metal-assisted exfoliation of few-layer black phosphorus with high yield.

We introduce a metal-assisted exfoliation method to produce few-layer black phosphorus with the lateral size larger than 50 μm and the area 100 times larger than those exfoliated using the normal "scotch-tape" technique. Using a field effect transistor it was found the hole mobility is 68.6 cm2 V-1 s-1 and the current on/off ratio can reach about 2 × 105.

High Performance Black Phosphorus Electronic and Photonic Devices with HfLaO Dielectric

As an emerging two-dimensional material, few-layer black phosphorus (BP) shows great potential in nanoelectronics and nanophotonics due to its high carrier velocity. However, non-optimized gate dielectrics often degrade the performance of BP devices severely. In this letter, we demonstrate high-performance BP devices using a novel HfLaO as back gate dielectric with improved interface quality. High current exceeding 1.15 mA/ $\mu \text{m}$ has been achieved at 20 K for BP transistors with improved noise spectral density. Moreover, BP photodetectors with a record high photoresponsivity up to $1.5\times 10^{8}$ A/W and fast response time of $10~\mu \text{s}$ at 300 K are demonstrated. Excellent photoresponse in a broadband spectrum range from 514 to 1800 nm at 70 K has also been achieved.

A novel electrically controllable volatile memory device based on few-layer black phosphorus

Exploiting the unique property of two dimensional material black phosphorus (BP), we theoretically propose a novel volatile memory device based on pure few-layer BP from atomic first principles calculations.

New solvent-stabilized few-layer black phosphorus for antibacterial applications.

Discovering highly efficient, environmentally friendly, and low-cost exfoliating media that can both disperse and protect black phosphorus (BP) remains a challenge. Herein, we demonstrate such a new molecule, N,N'-dimethylpropyleneurea (DMPU), for effective exfoliation and dispersion of two-dimensional BP nanosheets. A very high exfoliation efficiency of up to 16% was achieved in DMPU, significantly surpassing other good solvents. Exfoliated flakes are free from structural disorder or oxidation. Nanosheets retain high stability in DMPU even after addition of 25 vol% of common solvents. The solvation shell appears to protect the nanosheets from reacting with water and air, more remarkably than the best solvent N-cyclohexyl-2-pyrrolidone reported so far. Molecular dynamics simulations of the exfoliation process show that DMPU is among the effective solvents, although energetically it does not appear as favorable as some other amides. We also demonstrate that our exfoliated BP nanosheets exhibit excellent antimicrobial activities against both Escherichia coli and Staphylococcus aureus, outperforming other common two-dimensional materials of graphene and MoS2, suggesting promise in biomedical applications.

Wrinkle-induced high sorption makes few-layered black phosphorus a superior adsorbent for ionic organic compounds

Wrinkle-induced high sorption makes few-layered black phosphorus a superior adsorbent for both cationic and anionic organic compounds.

Enhanced stability and performance of few-layer black phosphorus transistors by electron beam irradiation.

Few layer black phosphorus (BP) has recently emerged as a potential graphene analogue due to its high mobility and direct, appreciable, band gap. The fabrication and characterization of field effect transistors (FETs) involves exposure of the channel material to an electron beam (e-beam) in imaging techniques such as transmission electron microscopy (TEM) and scanning electron microscopy (SEM), and fabrication techniques like electron beam lithography (EBL). Despite this, the effect of e-beam irradiation on BP-FET performance has not been studied experimentally. In this work, we report the first experimental study on the impact of e-beam irradiation on BP-FETs. An electron beam is known to induce defects and structural changes in 2D materials like graphene, MoS2etc. resulting in the deterioration of the device quality. However, for BP-FETs, we observe an improvement in the on-current and carrier mobility (μ) along with a decrease in threshold voltage (Vth) on exposure to an e-beam with 15 keV energy for 80 seconds. These changes can be attributed to the capture of electrons by traps near the SiO2-BP interface and reduced BP surface roughness due to e-beam exposure. Hysteresis measurements and physical characterization (i.e. atomic force microscopy (AFM), X-ray photoelectron (XPS) and Raman spectroscopies) validate these mechanisms. Reduced hysteresis indicates occupation of the traps, AFM surface scans indicate reduced surface roughness and XPS data show a reduced phosphorus oxide (POx) peak immediately after exposure. Raman measurements indicate a probable structural change due to the interaction between e-beam and BP which could result in better stability.

Enhancing the ambient stability of few-layer black phosphorus by surface modification.

Based on high-throughput density functional theory calculations, we investigated the adsorption characteristics of various elements across the Periodic Table on few-layer black phosphorus (BP). Using the criterion that the ratio of adsorption energy (Eads) to bulk cohesive energy (Ecoh) is greater than one (Eads/Ecoh > 1), we selected fifteen elements. The adsorption of these elements on few-layer BPs could significantly shift their conduction-band minimum (CBM) downward, suggesting the possibility of preventing the few-layer BPs from oxidation if the CBM can be shifted below the O2/O2− redox potential. Our study offers an efficient approach to overcoming the technical barrier in the practical application of few-layer BPs by enhancing its ambient stability via surface modification.

Electronic and optical properties of monolayer black phosphorus induced by bi-axial strain

Black phosphorus (BP) is a new two-dimensional (2D) material. It has received significant attention because of its great potential in the field of optoelectronics, which arises due to its low-dimensional effects. In this paper, the effect of bi-axial strain on the band structure of monolayer BP has been studied by using the first-principles method based on density functional theory (DFT). We find that the band gap range of monolayer BP can be moderately and effectively adjusted by external stress from 0 to 1.845 eV. Simultaneously, the direct band gap is maintained during the stretching process, which leads to a high electron mobility suitable for applications. Moreover, the compressive strain can result in a semiconductor–metal transition (SMT) with few-layer BP, whereas tensile strain only affects the band gap. Based on the electronic properties of monolayer BP, its optical properties are analyzed in detail, and the influence of strain—from a compressive strain of 12% to a tensile strain of 12%—on these properties is systematically discussed. It is found that the strain range and mode have a significant impact on the optical properties. In addition, the dielectric function and absorption spectra calculated along two different directions indicate that a significant optical anisotropy appears, giving a strong directionality dependence in the primitive and strained monolayer BP. It can be concluded that by applying external stress to monolayer BP, its optical properties can be readily controlled, which is beneficial for device applications. Furthermore, based on its direction-dependent response to the external stress, this behavior can also be used to detect the orientation of the deposited BP without the need for precise electron microscopy.

Integer and Fractional Quantum Hall effect in Ultrahigh Quality Few-layer Black Phosphorus Transistors.

As a high mobility two-dimensional semiconductor with strong structural and electronic anisotropy, atomically thin black phosphorus (BP) provides a new playground for investigating the quantum Hall (QH) effect, including outstanding questions such as the functional dependence of Landau level (LL) gaps on magnetic field B, and possible anisotropic fractional QH states. Using encapsulated few-layer BP transistors with mobility up to 55 000 cm2/(V s), we extracted LL gaps over an exceptionally wide range of B for QH states at filling factors -1 to -4, which are determined to be linear in B, thus resolving a controversy raised by its anisotropy. Furthermore, a fractional QH state at ν ≈ -4/3 and an additional feature at -0.56 ± 0.1 are observed, underscoring BP as a tunable 2D platform for exploring electron interactions.

Brittle-to-ductile transition in fracture of few-layered black phosphorus ribbons under uniaxial stretching

Owing to excellent electrical properties, few-layered black phosphorene (BP) ribbons will be wide used in nano-electro-mechanical systems. Before acting as a component in the nanosystem, they should be fabricated successfully. During peeling, pulling or cutting in fabrication of a few-layered BP ribbon, the load on it should be controlled to be less than its strength or ultimate strain. Otherwise, the ribbon will be broken which means a failed fabrication. For a deep understanding of the damage process, molecular dynamics simulations are adopted to illustrate the fracture of a few-layered BP ribbon under uniaxial stretching. Influence of both temperature and the thickness of the ribbon are discussed. The brittle-to-ductile transition of the three-dimensional fracture mode is discovered, and the mechanism is revealed.

Gate-tunable strong-weak localization transition in few-layer black phosphorus

Atomically-thin black phosphorus (BP) field-effect transistors show strong-weak localization transition, which is tunable through gate voltages. Hopping transports through charge impurity-induced localized states are observed at low carrier density regime. Variable-range hopping model is applied to simulate scattering behaviors of charge carriers. In the high carrier concentration regime, a negative magnetoresistance indicates weak localization effects. The extracted phase coherence length is power-law temperature-dependent and demonstrates inelastic electron–electron interactions and the 2D transport features in few-layer BP field-effect devices. The competition between localization and phase coherence lengths is investigated and analyzed based on observed gate-tunable strong-weak localization transition in few-layer BP.

Passively Q-switched wavelength-tunable 1-μm fiber lasers with tapered-fiber-based black phosphorus saturable absorbers

Abstract In this paper, we demonstrated passively Q-switched wavelength-tunable 1-μm fiber lasers utilizing few-layer black phosphorus saturable absorbers. The few-layer BP was deposited onto the tapered fibers by an optically driven process. The wavelength tunability was achieved with a fiber Sagnac loop comprised of a piece of polarization maintaining fiber and a polarization controller. Stable Q-switching laser operations were observed at wavelengths ranging from 1040.5 to 1044.6 nm at threshold pump power of 220 mW. Maximal pulse energy of 141.27 nJ at a repetition rate of 63 kHz was recorded under pump power of 445 mW.

Black phosphorus saturable absorber for dual-wavelength polarization-locked vector soliton generation

We report the usage of few-layered black phosphorus (BP) as saturable absorbers (SAs) to achieve dual-wavelength vector solitons mode locking in an erbium-doped fiber laser for the first time, to our knowledge. The SA is fabricated based on liquid exfoliation method by incorporating BP nanosheets with polyvinyl alcohol. We have demonstrated that the saturable absorption of BP is polarization independent. The laser is capable of generating dual-wavelength polarization-locked vector solitons centered at ~1533 and ~1558 nm with the bandwidths of ~3.7 and ~6.9 nm simultaneously. The results indicate the potential applications of few-layered BP as broadband SAs in vector soliton pulses generation.

Few-Layered Black Phosphorus: From Fabrication and Customization to Biomedical Applications.

As a new kind of 2D material, black phosphorus has gained increased attention in the past three years. Although few-layered black phosphorus nanosheets (BPs) degrade quickly under ambient conditions to phosphate anions, which greatly hampers their optical and electronic applications, this property also makes BPs highly biocompatible and biodegradable, and is regarded as an advantage for various biomedical applications. This Concept summarizes the state-of-art progresses of BPs, from fabrication and surface modification to biomedical applications. It is expected that BPs with such fascinating properties will encourage more scientists to engage in expanding its biomedical applications by tackling the scientific challenges involved in their development.