Few-layer Black Phosphorus Research Articles

Overcoming volumetric capacitance-rate performance tradeoff with 0D/2D conductive carbon nitride/phosphorene heterostructure for flexible supercapacitor

Few-layer black phosphorus (FL-BP) is considered a rising star 2D material for flexible supercapacitors (FSCs) due to its exceptional properties, including mechanical flexibility and high active surface area. However, the disordered deposition of FL-BP nanoflakes often leads to face-to-face restacking, which diminishes the effective active area and ion transport channels. This poses a huge challenge in simultaneously achieving high volumetric capacitance and rate capability. To address this, a 3D porous 0D/2D FL-BP/conductive carbon nitride (FL-BP/c-CN) film has been developed. The introduction of 0D c-CN nanoparticles effectively prevents the restacking of FL-BP nanoflakes and expands the nanofluidic channels, thus facilitating charge transport and ions diffusion. Additionally, the highly conductive c-CN nanoparticles embedded into the FL-BP layers significantly improve overall conductivity. As a result, the FL-BP/c-CN film-based FSC demonstrates a remarkable rate performance, retaining 70% capacitance as the scan rate increases from 10 to 100 mV/s. Moreover, the incorporation of 0D c-CN nanoparticles increases the available space for charge accumulation, yielding a volumetric capacitance of 28.5 F/cm3 at a scan rate of 10 mV/s, which is three times higher than that of a pure FL-BP film electrode (9.2 F/cm3). This work presents an innovative approach for developing high-performance FL-BP-based FSCs.

Photocatalytic Activity of Heterostructures Based on Graphite-Like Carbon Nitride Modified with Few-Layer Black Phosphorus and Cobalt Phosphide in the Hydrogen Evolution Reaction

Photocatalytic Activity of Heterostructures Based on Graphite-Like Carbon Nitride Modified with Few-Layer Black Phosphorus and Cobalt Phosphide in the Hydrogen Evolution Reaction

Electrosynthesis of an Improbable Directly Bonded Phosphorene-Fullerene Heterodimensional Hybrid toward Boosted Photocatalytic Hydrogen Evolution.

Phosphorene and fullerene are representative two-dimensional (2D) and zero-dimensional (0D) nanomaterials respectively, constructing their heterodimensional hybrid not only complements their physiochemical properties but also extends their applications via synergistic interactions. This is however challenging because of their diversities in dimension and chemical reactivity, and theoretical studies predicted that it is improbable to directly bond C60 onto the surface of phosphorene due to their strong repulsion. Here, we develop a facile electrosynthesis method to synthesize the first phosphorene-fullerene hybrid featuring fullerene surface bonding via P-C bonds. Few-layer black phosphorus nanosheets (BPNSs) obtained from electrochemical exfoliation react with C60 2- dianion prepared by electroreduction of C60, fulfilling formation of the "improbable" phosphorene-fullerene hybrid (BPNS-s-C60). Theoretical results reveal that the energy barrier for formation of [BPNS-s-C60]2- intermediate is significantly decreased by 1.88 eV, followed by an oxidization reaction to generate neutral BPNS-s-C60 hybrid. Surface bonding of C60 molecules not only improves significantly the ambient stability of BPNSs, but also boosts dramatically the visible light and near-infrared (NIR) photocatalytic hydrogen evolution rates, reaching 1466 and 1039 μmol h-1 g-1 respectively, which are both the highest values among all reported BP-based metal-free photocatalysts.

Anisotropic Sensing Performance in a High-Sensitivity Surface Plasmon Resonance Sensor Based on Few-Layer Black Phosphorus.

Few-layer black phosphorus (FLBP) is a highly promising material for high sensitivity label-free surface plasmon resonance (SPR) sensors due to its exceptional electrical, optical, and mechanical properties. FLBP exhibits inherent anisotropy with different refractive indices along its two main crystal orientations, the zigzag and armchair axes. However, this anisotropic property is often overlooked in FLBP-based sensors. In this study, we conducted a comprehensive investigation of the SPR reflectivity and phase in a BK7-Ag-FLBP structure to understand the influence of the stacking sequence and the number of FLBP layers on the sensing performance. Clear resonant angle shifts caused by different stacking sequences of FLBP could be observed both theoretically and experimentally. In the theoretical study, the highest reflective and phase sensitivities were achieved with a 12-layer black phosphorus (BP) structure. The reflectivity sensitivity reached 287.9°/refractive index units (RIU) with the zz stacking 12-layer BP film exhibiting a sensitivity 76°/RIU higher than the ac stacking structure. Similarly, the phase sensitivity reached 1162°/RIU with the zz stacking 12-layer BP structure showing a sensitivity 276.9°/RIU higher than the ac stacking structure. The electric field distribution of the 12-layer BP structure with four different stacking sequences has also been analyzed. In the experiment study, the well-known Attenuated Total Reflection (ATR) θ-2θ SPR setup is utilized to detect the reflectivity and phase of BK7-Ag-FLBP structures. The FLBP samples with the same thickness but different stacking sequences show significant resonant angle shift (0.275°) and maximum phase difference variation (34.6°). The FLBP sample thickness and crystal orientations have been demonstrated using the angular-resolved polarized Raman spectroscopy (ARPRS). These theoretical and experimental results provide strong evidence that the stacking sequences of FLBP have a significant impact on the sensing performance of SPR sensors. By harnessing the anisotropic properties of materials like FLBP, novel structures of anisotropic-2D material-based SPR sensors could open up exciting possibilities for innovative applications.

Strain and stacking registry effects on the hyperbolicity of exciton polaritons in few-layer black phosphorus

Strain and stacking registry effects on the hyperbolicity of exciton polaritons in few-layer black phosphorus

Covalent Functionalization of Few-Layer Black Phosphorus by the Complex [NiBr2(phen)] (phen = 1,10-Phenanthroline)

Covalent Functionalization of Few-Layer Black Phosphorus by the Complex [NiBr2(phen)] (phen = 1,10-Phenanthroline)

Unified understanding to the rich electronic-structure evolutions of two-dimensional black phosphorus under pressure

The electronic-structure evolutions of few-layer black phosphorus (BP) under pressure shows a wealth of phenomena, such as the nonmonotonic change of direct gap at the Γ point, the layer-number dependence, and the distinct responses to normal and hydrostatic pressures. A full and unified understanding to these rich phenomena remains lacking. Here, we provide a unified understanding from the competition between quasibonding (QB) interactions and chemical bonding interactions. The former decreases while the latter increases the band gap under pressure and the origin can be correlated to different combinations of inter- and intralayer antibonding or bonding interactions at the band edges. More interestingly, the interlayer QB interactions are a coexistence of two categories of interactions, namely, the coexistence of interactions between bands of the same occupancy (occupied-occupied and empty-empty interactions) and of different occupancies (occupied-empty interaction); and, the overall effect is a four-level interaction, which explains the anomalous interlayer-antibonding feature of the conduction band edge of bilayer BP. Our current study lays the foundation for the electronic-structure tuning of two-dimensional (2D) BP, and, our analysis method for multi-energy-level interactions can be applied to other 2D semiconductor homo- and heterostructures that have occupied-empty interlayer interactions. Published by the American Physical Society 2024

Laser-Synthesized Ru-Anchored Few-Layer Black Phosphorus for Superior Hydrogen Evolution: Role of Acoustic Levitation.

Electrochemical water splitting, driven by processed catalysts, is the most reasonable method for hydrogen production. This study demonstrates an activation phenomenon with ruthenium (Ru) nanoclusters on few-layered black phosphorus (BP), greatly enhancing the electrocatalytic hydrogen evolution reaction (HER). Efficient BP exfoliation was achieved using acoustic levitators and pulsed laser irradiation in liquids (PLIL), yielding charge-transfer Ru-nanoclusters on modulated surfaces. Various PLIL parameters were examined for the optimal BP sheet size. After ruthenization, Ru's d-band center facilitated hydrogen adsorption via Ru-H bonding. Synergy between BP's charge-carrier properties and Ru's active sites boosted HER kinetics with an ultralow overpotential of 84 mV at 10 mA/cm2 in KOH. Additionally, the RuO2 || RuBP-2 electrolyzer demonstrated remarkable overall water splitting performance at ∼1.60 V at 10 mA/cm2. These results highlight the pivotal role of metal nanoclusters on exfoliated BP surfaces and offer a refined strategy for high-density electrocatalysts in energy conversion.

Sonochemically synthesized black phosphorus nanoparticles: a promising candidate for piezocatalytic antibacterial activity with enhanced dielectric properties.

The drawbacks inherent to traditional antibacterial therapies, coupled with the escalating prevalence of multi-drug resistant (MDR) microorganisms, have prompted the imperative need for novel antibacterial strategies. Accordingly, the emerging field of piezocatalysis in semiconductors harnesses mechanical stress to drive chemical reactions by utilizing piezo-generated free charge carriers, presenting a promising technology. To the best of our knowledge, this study is the first to provide a comprehensive overview of the eradication of pathogenic S. aureus bacteria using few-layer black phosphorus (SCBP) piezo catalyst under mechanical stimuli, along with the exploration of temperature dependent dielectric properties. The synthesis of the piezo catalysts involved a one-step cost-effective sonochemical method, and its structural, morphological, elemental, optical, and overall polarization properties were thoroughly characterized and compared with the traditional method-derived product (TABP). The synthesis-introduced defects, reduced crystalline diameters, modified bandgap (1.76 eV), nanoparticle aggregation, photoluminescence quenching, along with interfacial polarization, synergistically contribute to SCBP's exceptional dielectric response (4.596 × 107 @40 Hz), which in turn enhanced the piezocatalytic activity. When subjected to soft ultrasound stimulation at 15 kHz, the piezo catalyst SCBP demonstrated significant ROS-mediated antibacterial activity, resulting in a ∼94.7% mortality rate within 40 minutes. The impact of this study extends to cost-effective energy storage devices and advances in antibacterial therapy, opening new dimensions in both fields.

An updated review of few-layer black phosphorus serving as a promising photocatalyst: synthesis, modification and applications.

Semiconductor photocatalysts represent a potential strategy to simultaneously solve the global energy shortage and environmental pollution, and black phosphorus (BP) has gained widespread applications in photocatalysis due to its high hole mobility, strong light trapping capabilities, and adjustable band gap. Nevertheless, the original material exhibits unsatisfactory photocatalytic activity in terms of low carrier separation efficiency, weak environmental stability, and difficult to control layer thickness. The following review briefly presents the fundamental characteristics and extensively discusses the synthesis methods and modification strategies for few-layer black phosphorus (FL-BP). Furthermore, various applications of composite photocatalysts derived from FL-BP such as water splitting, pollutant degradation, the carbon dioxide reduction reaction (CO2RR), phototherapy, bacterial disinfection, N2 fixation, and hydrogenation reactions are reviewed. Finally, the opportunities and challenges for the development and further investigation of advanced FL-BP-based photocatalysts are also presented.

Electronic thermal conductivity of few-layer black phosphorus

The theoretical investigations of anisotropic electronic thermal conductivity of nanoscale black phosphorus along zigzag and armchair directions are presented. Electrons in black phosphorus assumed to be scattered by in-plane linear dispersion phonons and out-of-plane quadratic dispersion phonons via deformation potential couplings. The individual contributions from in-plane phonon and out-of-plane phonon processes to the electronic thermal conductivity show dominant role of in-plane phonon processes. The anisotropic behaviour of electronic thermal conductivity is noticed and found to be sensitive to the carrier density and temperature. Role and relative importance of anisotropic electronic thermal conductivity in the analysis of experimental thermal conductivity data of nanoscale black phosphorus samples is investigated.

Optical tuning of the terahertz response of black phosphorus quantum dots: effects of weak carrier confinement

Abstract In contrast to few-layer black phosphorus (BP) with a relatively larger area, BP quantum dots (BP-QDs) are expected to have distinctive electromagnetic response and carrier behaviors, especially in low-frequency range such as in the THz regime. Herein, we experimentally investigate the THz properties of BP-QDs as well as the optical control of these properties. It is demonstrated that the effects of weak carrier confinement, which is associated with diffusive restoring current in each BP-QD, contribute significantly to the effective THz conductivity of BP-QDs. Instead, spectral features of discretely spaced energy levels as shown for many kinds of semiconductor QDs in UV-visible range are not observed in the THz regime. This indicates an insignificant contribution of strong quantum confinement here. Based on the modified Drude–Smith formula, we show that the optical excitation/pump of a CW laser can induce photogenerated carriers and enhance the effects of weak carrier confinement in BP-QDs. Thus, a nonlinear enhancement of THz absorption can be observed by increasing the power of the excitation laser. These results not only deepen our understanding of the fundamental physics of BP nanomaterials but also provide an alternative approach to realize active control of BP-based THz devices.

Edge-selective covalent passivation of black phosphorus nanosheets by fullerene C70 toward enhanced antimicrobial performance

In the fight against bacterial infection, conventional antibiotic treatment encounters the formidable challenges of drug resistance and sluggish development. Non-metallic two-dimensional (2D) nanomaterials such as black phosphorus (BP) have emerged as promising non-antibiotic antimicrobial candidates due to its peculiar physiochemical properties, but face hurdles including low ambient stability and limited antibacterial activity, hindering its widespread utilization in disinfection. Herein, few-layer BP nanosheets (BPNSs) were covalently passivated by edge-selectively grafting fullerene C70 via a one-step solid-state mechanochemical route, and for the first time the covalently functionalized BPNSs is employed in disinfection. Fullerene edge-selective covalent passivation not only effectively overcomes the obstacles of poor ambient stability, but also substantially enhances the antibacterial activities of BPNSs. The BPNSs-C70 hybrid (denoted as BPNSs-C70) was applied as a novel non-metallic and non-antibiotic nano-antibacterial agent. Under 660 nm visible light irradiation, BPNSs-C70 demonstrates high generation capacity of reactive oxygen species (ROS), resulting in boosted in vitro and in vivo antibacterial efficacies against methicillin-resistant Staphylococcus aureus (MRSA) relative to the pristine BPNSs with exceptional biocompatibility. The significantly enhanced antibacterial performance of BPNSs-C70 is attributed to the synergistically improved singlet oxygen (1O2) and hydroxyl radicals (•OH) generation originated from the intramolecular electron transfer from BPNSs to C70.

Charge transfer interfaces across black phosphorus/Co, N Co-doped carbon heterojunction for enhanced electrocatalytic water splitting

The practicality of electrochemical water-splitting technology relies on the development of novel and efficient bifunctional electrocatalysts capable of facilitating both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Black phosphorus (BP) holds tremendous promise for HER and OER electrocatalysis owing to its fully exposed atoms and high carrier mobility. However, the electrocatalytic performance of BP is still much lower than the expected theoretical limit, presenting an exciting challenge for further advancements. Herein, we embed electrochemically exfoliated few-layer BP nanosheets in higher Fermi level (EF) of cobalt, nitrogen co-doped carbons to form a new heterojunction (CoNC-BP), as efficient bifunctional electrocatalysts toward HER and OER for the advancement overall water splitting applications. A directed interfacial electron transfer is realized from CoNC to BP, facilitated by the lowering Fermi level (EF). This interfacial electron transfer plays a crucial role in optimizing the adsorption and desorption of active intermediates, while also introducing an abundance of hypervalent Co sites. These factors collectively contribute to the remarkable electrocatalytic activities of HER and OER performance, leading to the efficient performance of the developed CoNC-BP heterojunction in water-splitting applications. This work demonstrates a promising breakthrough that can inspire the design of high-efficiency catalysts.

Layer-dependent exciton polarizability and the brightening of dark excitons in few-layer black phosphorus

The evolution of excitons from 2D to 3D is of great importance in photo-physics, yet the layer-dependent exciton polarizability hasn’t been investigated in 2D semiconductors. Here, we determine the exciton polarizabilities for 3- to 11-layer black phosphorus—a direct bandgap semiconductor regardless of the thickness—through frequency-resolved photocurrent measurements on dual-gate devices and unveil the carrier screening effect in relatively thicker samples. By taking advantage of the broadband photocurrent spectra, we are also able to reveal the exciton response for higher-index subbands under the gate electrical field. Surprisingly, dark excitons are brightened with intensity even stronger than the allowed transitions above certain electrical field. Our study not only sheds light on the exciton evolution with sample thickness, but also paves a way for optoelectronic applications of few-layer BP in modulators, tunable photodetectors, emitters and lasers.

Tailoring optical constants of few-layer black phosphorus coatings: Spectroscopic ellipsometry approach supported by ab-initio simulation

2D black phosphorus (BP) has attracted extensive attention as an anisotropic platform for novel optoelectronic and polarizing optics applications. Insight into the factors that tune the optical and polarizing properties of 2D BP reveals their essential influence on BP-based photonic and optoelectronic devices. In this work, studies of the optical constants of few-layer black phosphorus coatings are studied and discussed, with particular emphasis on the complex dielectric function. Herein, the complex optical constants of multi-flake composite films in the energy range of 1.38–6.2 eV by spectroscopic ellipsometry with the use of the classical optical model have been determined. Classical optical simulations were supplied by dielectric function estimations delivered by density functional theory. Additionally, few-layer black phosphorus coatings were imaged by polarizing microscopy and investigated by Raman spectroscopy, revealing a size-tunable flake composition. The pattern analysis of the polarization images reveals a shift in polarization anisotropy originated mainly from the central region of the flake. The semi-isotropic optical properties suggest that the extinction coefficient of BP flakes defines the applications of BP in photonics, waveguides, and directional optoelectronic devices.

Electronic Structure of Few-Layer Black Phosphorus from μ-ARPES.

Black phosphorus (BP) stands out among two-dimensional (2D) semiconductors because of its high mobility and thickness dependent direct band gap. However, the quasiparticle band structure of ultrathin BP has remained inaccessible to experiment thus far. Here we use a recently developed laser-based microfocus angle resolved photoemission (μ-ARPES) system to establish the electronic structure of 2-9 layer BP from experiment. Our measurements unveil ladders of anisotropic, quantized subbands at energies that deviate from the scaling observed in conventional semiconductor quantum wells. We quantify the anisotropy of the effective masses and determine universal tight-binding parameters, which provide an accurate description of the electronic structure for all thicknesses.

A Superior Two-Dimensional Phosphorus Flame Retardant: Few-Layer Black Phosphorus

The usage of flame retardants in flammable polymers has been an effective way to protect both lives and material goods from accidental fires. Phosphorus flame retardants have the potential to be follow-on flame retardants after halogenated variants, because of their low toxicity, high efficiency and compatibility. Recently, the emerging allotrope of phosphorus, two-dimensional black phosphorus, as a flame retardant has been developed. To further understand its performance in flame-retardant efficiency among phosphorus flame retardants, in this work, we built model materials to compare the flame-retardant performances of few-layer black phosphorus, red phosphorus nanoparticles, and triphenyl phosphate as flame-retardant additives in cellulose and polyacrylonitrile. Aside from the superior flame retardancy in polyacrylonitrile, few-layer black phosphorus in cellulose showed the superior flame-retardant efficiency in self-extinguishing, ~1.8 and ~4.4 times that of red phosphorus nanoparticles and triphenyl phosphate with similar lateral size and mass load (2.5~4.8 wt%), respectively. The char layer in cellulose coated with the few-layer black phosphorus after combustion was more continuous and smoother than that with red phosphorus nanoparticles, triphenyl phosphate and blank, and the amount of residues of cellulose coated with the few-layer black phosphorus in thermogravimetric analysis were 10 wt%, 14 wt% and 14 wt% more than that with red phosphorus nanoparticles, triphenyl phosphate and blank, respectively. In addition, although exothermic reactions, the combustion enthalpy changes in the few-layer black phosphorus (−127.1 kJ mol−1) are one third of that of red phosphorus nanoparticles (−381.3 kJ mol−1). Based on a joint thermodynamic, spectroscopic, and microscopic analysis, the superior flame retardancy of the few-layer black phosphorus was attributed to superior combustion reaction suppression from the two-dimensional structure and thermal nature of the few-layer black phosphorus.

Angular resolved ultra-low frequency Raman spectroscopy of few-layer black phosphorous

Few-layer black phosphorus (FLBP) exhibits valuable mechanical, optical, and electronic properties for potential applications in nanodevices, ranging from insulators to superconductors. In particular, their band structure and optical properties are closely related to layer numbers, stacking sequences, and twist angles. However, the mechanism behind these factors is not fully understood, as it is quite difficult to obtain stacking details using non-destructive probes. This article provides direct experimental evidence of the weak interlayer van der Waals (vdW) interaction of FLBP using a state-of-the-art, angular resolved, ultra-low frequency Raman spectroscopy system. A modified linear-chain model is presented to evaluate the layer number dependence on the extremely low-frequency breathing modes (Ag3 and Ag4). The polarization analysis illustrates that most bi-layer BP samples prefer the AB stacking sequence. Furthermore, the stacking angle of bi-layer BP was assigned based on its minimum intensity of Ag3 and Ag4 modes. This investigation on angular resolved extremely low-frequency Raman spectra sheds light on a new approach for analyzing the stacking details of FLBP, which is of great significance for developing novel FLBP-based nanodevices.

Enhanced degradation of few-layer black phosphorus by fulvic acid: Processes and mechanisms

The oxidation of the emerging nanomaterial black phosphorus (BP) affected by pH and oxygen has been carefully documented. However, in natural waters, there is a large amount of chemically reactive organic matters like fulvic acid (FA), whose impacts on degradation and stability of few-layer BP or BP nanosheets (BPNS) are scarcely disclosed. Hence, we investigated the kinetics of BPNS degradation products (H2PO2−, HPO32−, and PO43−) in the presence of FA. The results showed that the apparent reaction rate constants of BPNS were 0.026, 0.050, and 0.060 d−1 under oxygen-and-light condition and 0.005, 0.016, and 0.023 d−1 under hypoxia-and-darkness condition at FA gradients of 0, 2.5, and 5 mgC/L, respectively. Microscopic observations, simple molecular simulation experiment, and density functional theory computation explained that FA significantly enhanced the degradation of P atoms on the BPNS surface through the indirect pathway of reducing the energy barrier of O2 dissociative adsorption and the direct pathway of chemical adsorption, which caused the P-P bond on the BPNS surface to break down and formed P-O bonds or C-P bonds. This study revealed for the first time the degradation mechanism of BPNS in the presence of FA, which is a chemical mechanism of the BPNS transformation behavior. It helps to make a more scientific risk assessment of BP in natural waters.