Ternary Nanowires Research Articles

Modeling the Composition of III–V Ternary Nanowires with Group V Depletion

Modeling the Composition of III–V Ternary Nanowires with Group V Depletion

Magnetic properties of bamboo-like Ni-Zn-in nanowires using 3D-AAO templates

In this paper, using three-dimensional porous alumina (3D-AAO) as a template, Ni-Zn-In nanowires array with periodically changing diameters was successfully prepared by direct current electrodeposition method. The effect of deposition voltage on the morphology, crystal structure and magnetic properties of Ni-Zn-In ternary alloy nanowires was studied. The experimental results show that the diameters of the nanowires are 212 nm and 151 nm, and the periodic length is 800 nm, which matches the pore size of the phosphoric acid-etched 3D-AAO template. XRD results indicate that the crystal structure of Ni-Zn-In nanowires can be adjusted by the deposition voltage. The VSM results reveal that the Ni-Zn-In nanowires possess soft magnetic properties and significant magnetic anisotropy, with the easy magnetization direction parallel to the film. The nanowires deposited at −1.5 V exhibit the highest coercivity of 161 Oe and squareness of 0.045. Micromagnetic simulations show that the magnetization reversal mechanism of the Ni-Zn-In nanowires is localized nucleation mode.

Ultrathin ternary PtNiRu nanowires for enhanced oxygen reduction and methanol oxidation catalysis via d-band center regulation

Direct methanol fuel cells rely on the efficiency of their anode/cathode electrocatalysts to facilitate the methanol oxidation reaction and oxygen reduction reaction, respectively. Platinum-based nanocatalysts are at the forefront due to their superior catalytic properties. However, the high-cost, scarcity, and low CO tolerance of platinum pose challenges for the scalable application of DMFCs. Herein, we report novel ultrathin ternary PtNiRu alloy nanowires to improve Pt utilization and CO tolerance. These novel electrocatalysts incorporate the oxophilic metal Ru into ultrathin PtNi nanowires, aiming to enhance the intrinsic activity of platinum while leveraging the long-term durability and high utilization efficiency provided by the bimetallic synergistic effect. The PtNiRu NWs significantly enhance both mass activity and specific activity for ORR, performing about 6.9 times and 3.9 times better than commercial Pt/C, respectively. After a rigorous durability test of 10,000 cycles, the PtNiRu NWs only exhibited a 25.2 % loss in mass activity. Additionally, for MOR, the MA and SA of PtNiRu NWs exceed that of Pt/C catalyst by 4.30 and 2.72 times, respectively, and exhibit exceptional resistance to CO poisoning. Theoretical insights from density functional theory calculations suggest that the introduction of Ru modulates the d-band center of the surface Pt atoms, which contributes to decreased binding strength of oxygenated species and an elevated dissolution potential, substantiating the enhanced performance metrics, and the durability enhancement stems from the stronger PtM bonds than those in PtNiRu NWs resulted from PtRu covalent interactions. These findings not only provide a new perspective on platinum-based nanocatalysts but also significantly advance the quest for more efficient and durable electrocatalysts for DMFCs, representing a substantial stride in fuel cell technology.

High-Performance Ultraviolet to Near-Infrared Antiambipolar Photodetectors Based on 1D CdSxSe1-x/2D Te Heterojunction.

Antiambipolar heterojunctions are regarded as a revolutionary technology in the fields of electronics and optoelectronics, enabling the switch between positive and negative transconductance within a single device, which is crucial for diverse logic circuit applications. This study pioneers a mixed-dimensional photodetector featuring antiambipolar properties, facilitated by the van der Waals integration of one-dimensional CdSxSe1-x nanowires and two-dimensional Te nanosheets. This antiambipolar device enables flexible control over carrier transport via gate voltage, thus paving new paths for future optoelectronic devices. Furthermore, by precisely managing the stoichiometry of the ternary alloy CdSxSe1-x nanowires, fine-tuning of the nanowire band structure is achieved. This allows for customizable heterojunction band alignment (Type I and Type II), enabling adjustable band alignment. Through sophisticated band engineering, optimal Type II band alignment is achieved at the CdSxSe1-x/Te interface, significantly enhancing the device's photoelectric conversion efficiency through the synergistic effect of different dimensional materials. Exhibiting outstanding photoresponse across a broad spectral range from ultraviolet to near-infrared, especially under 450 nm illumination, the CdSxSe1-x/Te heterojunction photodetector demonstrates superior performance, including an impressive responsivity of 284 A W-1, a high detectivity of 1.07 × 1017 Jones, an elevated external quantum efficiency of 7.83 × 104 %, and a swift response time of 11 μs. Ultimately, this customizable antiambipolar photodetector lays a solid foundation for the advancement of next-generation optoelectronic technologies.

Interplay of Kinetic and Thermodynamic Factors in the Stationary Composition of Vapor-Liquid-Solid IIIVxV1-x Nanowires.

Compositional control over vapor-liquid-solid III-V ternary nanowires based on group V intermix (VLS IIIVxV1-x NWs) is complicated by the presence of a catalyst droplet with extremely low and hence undetectable concentrations of group V atoms. The liquid-solid and vapor-solid distributions of IIIVxV1-x NWs at a given temperature are influenced by the kinetic parameters (supersaturation and diffusion coefficients in liquid, V/III flux ratio in vapor), temperature and thermodynamic constants. We analyze the interplay of the kinetic and thermodynamic factors influencing the compositions of VLS IIIVxV1-x NWs and derive a new vapor-solid distribution that contains only one parameter of liquid, the ratio of the diffusion coefficients of dissimilar group V atoms. The unknown concentrations of group V atoms in liquid have no influence on the NW composition at high enough levels of supersaturation in liquid. The simple analytic shape of this vapor-solid distribution is regulated by the total V/III flux ratio in vapor. Calculating the temperature-dependent desorption rates, we show that the purely kinetic regime of the liquid-solid growth occurs for VLS IIIVxV1-x NWs in a wide range of conditions. The model fits the data well on the vapor-solid distributions of VLS InPxAs1-x and GaPxAs1-x NWs and can be used for understanding and controlling the compositions of any VLS IIIVxV1-x NWs, as well as modeling the compositional profiles across NW heterostructures in different material systems.

Enhanced efficiency and stability of dye-sensitized solar cells utilizing FeCo2S4 nanowires as Pt-free counter electrodes

Replacing traditional Pt-based counter electrodes with low-cost and highly stable materials is crucial for the development of commercially viable dye-sensitized solar cells (DSSCs). In this study, we synthesized a ternary Pt-free FeCo2S4 nanowire (NW)-based sulfide electrocatalyst by a three-step solvothermal method. This material was then used as a counter electrode in DSSCs to facilitate the reduction of triiodide species. The formation of FeCo2S4 NW was confirmed by various characterization techniques such as X-ray diffraction, energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Scanning electron microscopy analysis revealed the structure of the nanowires. Electrochemical studies, which included cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization methods, revealed the excellent stability, superior electrocatalytic activity and remarkable kinetics of FeCo2S4 NW in the reduction of triiodide to iodide. Photovoltaic measurements of the fabricated DSSCs yielded a power conversion efficiency (PCE) of 7.88 % for the FeCo2S4-based devices, outperforming the control device made of Pt (PCE=7.45 %). This improvement was primarily due to the increase in short-circuit current density (JSC), thanks to the lower charge transfer resistance (RCT) of FeCo2S4 NW (JSC=15.23 mA/cm2; RCT=5.54 Ω cm2) compared to Pt (JSC=14.12 mA/cm2; RCT=7.07 Ω cm2). In addition, the FeCo2S4 NW-based solar cells exhibited excellent stability and maintained their high PCE value even after 10 days of aging under ambient conditions, while Pt-based DSSCs showed a 3 % decrease from their initial PCE value. This FeCo2S4 NW counter electrode proves to be an excellent alternative to Pt, and the presented results provide valuable insights for the development of cost-effective and highly stable DSSCs.

Ionic-storage capacitance enhanced by a self-assembled CoO-Nafion nanocoating on single-walled carbon nanotubes

We introduce a novel approach for enhancing ion-storage capabilities through the self-assembled formation of ternary nanowires, consisting of a CoO-and-Nafion nanocomposite encasing metallic single-walled carbon nanotubes (SWNTs). These nanowires highlight the indispensable role of the conductor-semimetallic SWNT-CoO heterojunction in expediting the redox reaction kinetics of the CoO while the Nafion component facilitates the transport of hydroxide ions. Consequently, supercapacitors comprising the ternary nanowires deliver the specific capacitance of calculated 18.84 mF cm−2, five times higher than those obtained at the counterpart devices that lack Nafion and/or CoO. This self-assembly method precisely organizes functional components within the nanowires, aligning with electrochemical principles to optimize charge transfer and minimize concentration gradients for improved electrochemical polarization. Our function-enhanced ternary nanowires, together with their straightforward synthetic process, promise an alternative opportunity for formulating high-performance ion-storage electrodes and thus pave the way for their application in next-generation supercapacitor technologies.

Well-defined ternary metal phosphide nanowires with stabilized Pt nanoclusters to boost alkaline hydrogen evolution reaction

Designing low-content and high-activity Pt-based catalysts with the high durability for the electrochemical hydrogen production remains a challenge. In this study, a ternary metal phosphide (NiCoP) with 1D nanowire (NW) and 2D nanosheet (NS) morphologies incorporating Pt clusters (denoted as Ptcluster-NiCoP@NF NWs and Ptcluster-NiCoP@NF NSs, respectively) was prepared using a hydrothermal–phosphorization–electrodeposition method. Based on the “tip effect” of NWs and a high electrochemical surface area, the as-prepared Ptcluster-NiCoP@NF NWs display better hydrogen evolution reaction (HER) performance, with a low overpotential of 65 mV at a high current density of 100 mA cm−2 and a low Tafel slope of 38.86 mV dec−1, than the Ptcluster-NiCoP@NF NSs, with an overportential of 95 mV at 42.53 mV dec−1. This indicates that the NiCoP NW-based support exhibits faster HER kinetics. The mass activity (11.47 A mgPt−1) of the Ptcluster-NiCoP@NF NWs is higher than that of commercial Pt/C catalysts. Significantly, the Ptcluster-NiCoP@NF NWs display excellent cyclic stability with negligible losses for 5000 cycles and 30-h tests at a high current of 500 mA cm−2.

Low-threshold single ternary GaAsSb nanowire lasers emitting at silicon transparent wavelengths

Conventional binary III–V nanowire (NW) lasers face substantial challenges in tuning their lasing emission to silicon transparent wavelengths and require complex quantum heterostructure designs for realizing on-chip integrated nanolasers. Here, an alternative and straightforward approach is reported by developing ternary III–V NW-lasers in the form of surface-passivated GaAsSb NW-lasers grown on silicon. High-quality GaAsSb NW-cavities with high Sb-content (>20%) and extended lengths (>5 μm) are shown to exhibit striking radiative efficiency enhancements (∼200-fold) when passivated by closely lattice-matched InAlGaAs shell layers. Utilizing this core–shell approach, optically pumped lasing is then demonstrated from single GaAsSb NW-lasers with lasing threshold as low as 3.2 μJ/cm2 at temperatures up to 250 K and emission wavelengths of ∼1.1–1.2 μm. Analysis of the optical mode spectra and mode-dependent threshold gain further shows that lasing is induced by the fundamental HE11 modes, and likely even lower thresholds may be achieved by establishing the TE01 mode at increased NW-cavity diameters.

Circumventing the Uncertainties of the Liquid Phase in the Compositional Control of VLS III-V Ternary Nanowires Based on Group V Intermix.

Control over the composition of III-V ternary nanowires grown by the vapor-liquid-solid (VLS) method is essential for bandgap engineering in such nanomaterials and for the fabrication of functional nanowire heterostructures for a variety of applications. From the fundamental viewpoint, III-V ternary nanowires based on group V intermix (InSbxAs1-x, InPxAs1-x, GaPxAs1-x and many others) present the most difficult case, because the concentrations of highly volatile group V atoms in a catalyst droplet are beyond the detection limit of any characterization technique and therefore principally unknown. Here, we present a model for the vapor-solid distribution of such nanowires, which fully circumvents the uncertainties that remained in the theory so far, and we link the nanowire composition to the well-controlled parameters of vapor. The unknown concentrations of group V atoms in the droplet do not enter the distribution, despite the fact that a growing solid is surrounded by the liquid phase. The model fits satisfactorily the available data on the vapor-solid distributions of VLS InSbxAs1-x, InPxAs1-x and GaPxAs1-x nanowires grown using different catalysts. Even more importantly, it provides a basis for the compositional control of III-V ternary nanowires based on group V intermix, and it can be extended over other material systems where two highly volatile elements enter a ternary solid alloy through a liquid phase.

Sb-saturated high-temperature growth of extended, self-catalyzed GaAsSb nanowires on silicon with high quality

Ternary GaAsSb nanowires (NW) are key materials for integrated high-speed photonic applications on silicon (Si), where homogeneous, high aspect-ratio dimensions and high-quality properties for controlled absorption, mode confinement and waveguiding are much desired. Here, we demonstrate a unique high-temperature (high-T >650 °C) molecular beam epitaxial (MBE) approach to realize self-catalyzed GaAsSb NWs site-selectively on Si with high aspect-ratio and non-tapered morphologies under antimony (Sb)-saturated conditions. While hitherto reported low-moderate temperature growth processes result in early growth termination and inhomogeneous morphologies, the non-tapered nature of NWs under high-T growth is independent of the supply rates of relevant growth species. Analysis of dedicated Ga-flux and growth time series, allows us to pinpoint the microscopic mechanisms responsible for the elimination of tapering, namely concurrent vapor–solid, step-flow growth along NW side-facets enabled by enhanced Ga diffusion under the high-T growth. Performing growth in an Sb-saturated regime, leads to high Sb-content in VLS-GaAsSb NW close to 30% that is independent of Ga-flux. This independence enables multi-step growth via sequentially increased Ga-flux to realize uniform and very long (>7 μm) GaAsSb NWs. The excellent properties of these NWs are confirmed by a completely phase-pure, twin-free zincblende (ZB) crystal structure, a homogeneous Sb-content along the VLS-GaAsSb NW growth axis, along with remarkably narrow, single-peak low-temperature photoluminescence linewidth (<15 meV) at wavelengths of ∼1100–1200 nm.

Composition of Vapor-Liquid-Solid III-V Ternary Nanowires Based on Group-III Intermix.

Compositional control in III-V ternary nanowires grown by the vapor-liquid-solid method is essential for bandgap engineering and the design of functional nanowire nano-heterostructures. Herein, we present rather general theoretical considerations and derive explicit forms of the stationary vapor-solid and liquid-solid distributions of vapor-liquid-solid III-V ternary nanowires based on group-III intermix. It is shown that the vapor-solid distribution of such nanowires is kinetically controlled, while the liquid-solid distribution is in equilibrium or nucleation-limited. For a more technologically important vapor-solid distribution connecting nanowire composition with vapor composition, the kinetic suppression of miscibility gaps at a growth temperature is possible, while miscibility gaps (and generally strong non-linearity of the compositional curves) always remain in the equilibrium liquid-solid distribution. We analyze the available experimental data on the compositions of the vapor-liquid-solid AlxGa1-xAs, InxGa1-xAs, InxGa1-xP, and InxGa1-xN nanowires, which are very well described within the model. Overall, the developed approach circumvents uncertainty in choosing the relevant compositional model (close-to-equilibrium or kinetic), eliminates unknown parameters in the vapor-solid distribution of vapor-liquid-solid nanowires based on group-III intermix, and should be useful for the precise compositional tuning of such nanowires.

Self-Supported 3D PtPdCu Nanowires Networks for Superior Glucose Electro-Oxidation Performance.

The development of non-enzymatic and highly active electrocatalysts for glucose oxidation with excellent durability for blood glucose sensors has aroused widespread concern. In this work, we report a fast, simple, and low-cost NaBH4 reduction method for preparing ultrafine ternary PtPdCu alloy nanowires (NWs) with a 3D network nanostructure. The PtPdCu NWs catalyst presents significant efficiency for glucose oxidation-reduction (GOR), reaching an oxidative peak-specific activity of 0.69 mA/cm2, 2.6 times that of the Pt/C catalyst (0.27 mA/cm2). Further reaction mechanism investigations show that the NWs have better conductivity and smaller electron transfer resistance. Density functional theory (DFT) calculations reveal that the alloying effect of PtPdCu could effectively enhance the adsorption energy of glucose and reduce the activation energy of GOR. The obtained NWs also show excellent stability over 3600 s through a chronoamperometry test. These self-supported ultrafine PtPdCu NWs with 3D networks provide a new functional material for building blood glucose sensors and direct glucose fuel cells.

Three-Dimensional WCoFe Ternary Metal Oxide Nanowire Network as a Carbon-Free Cathode Catalyst for High-Performance Li–O2 Batteries

Three-Dimensional WCoFe Ternary Metal Oxide Nanowire Network as a Carbon-Free Cathode Catalyst for High-Performance Li–O₂ Batteries

An Overview of Modeling Approaches for Compositional Control in III-V Ternary Nanowires.

Modeling of the growth process is required for the synthesis of III-V ternary nanowires with controllable composition. Consequently, new theoretical approaches for the description of epitaxial growth and the related chemical composition of III-V ternary nanowires based on group III or group V intermix were recently developed. In this review, we present and discuss existing modeling strategies for the stationary compositions of III-V ternary nanowires and try to systematize and link them in a general perspective. In particular, we divide the existing approaches into models that focus on the liquid-solid incorporation mechanisms in vapor-liquid-solid nanowires (equilibrium, nucleation-limited, and kinetic models treating the growth of solid from liquid) and models that provide the vapor-solid distributions (empirical, transport-limited, reaction-limited, and kinetic models treating the growth of solid from vapor). We describe the basic ideas underlying the existing models and analyze the similarities and differences between them, as well as the limitations and key factors influencing the stationary compositions of III-V nanowires versus the growth method. Overall, this review provides a basis for choosing a modeling approach that is most appropriate for a particular material system and epitaxy technique and that underlines the achieved level of the compositional modeling of III-V ternary nanowires and the remaining gaps that require further studies.

Ultrathin ternary PtNiGa nanowires for enhanced oxygen reduction reaction

Achieving high activity and durability for the oxygen reduction reaction (ORR) with an ultra-low amount of platinum is significant to promote the widespread application of proton exchange membrane fuel cells (PEMFCs). Here we report a new ultrathin (∼1 nm) ternary PtNiGa alloy nanowires (PtNiGa NWs) electrocatalyst, in which the presence of gallium (Ga) enhances the oxidation resistance of platinum (Pt) and nickel (Ni) and suppresses the dissolution of Ni. The mass and specific activities of PtNiGa NWs are about 11.2 and 7.6 times higher than those of commercial Pt/C catalysts for ORR. Moreover, the mass activity of PtNiGa/C NWs nanocatalyst decreased only by 12.8% and largely retained its electrochemical surface area (ECSA) after 10,000 potential cycles, compared with 38% loss of ECSA for commercial Pt/C catalyst. Therefore, this work provides a general guideline for preparing ternary alloy electrocatalysts and enhancing the activity and stability of the cathode ORR reaction of PEMFCs.

Controllable Synthesis of PtIrCu Ternary Alloy Ultrathin Nanowires for Enhanced Ethanol Electrooxidation.

Rational design and controllable synthesis of catalysts with unique structure and composition are effective ways to promote electrocatalytic ethanol oxidation, thus contributing the direct ethanol fuel cells to gain ground. Herein, 2.5 nm-thin PtIrCu ternary alloy ultrathin nanowires (UNWs) with high-density planar defects are synthesized via oriented attachment with the assistance of H2. By adjusting the contents of Ir and Cu atoms, we find that the structure of the products changed from nanowires (NWs) to nanoparticles with the increase of Ir content. Density functional theory calculations show that when Cu atoms are replaced by Ir atoms, the vacancy formation energy of Pt atoms is increased, making the Pt atoms difficult to be activated by H2, which is not conducive to the formation of a one-dimensional structure. The optimal Pt43Ir32Cu25 UNWs achieve excellent ethanol electrooxidation reaction activity (1.05 A·mg-1Pt and 1.67 mA·cm-2), for it can significantly reduce the onset potential and improve the ability of CO anti-poisoning. The significant improvement in catalytic performance is attributed to the synergistic effect of the alloy and the NW structure with high-density planar defects.

1D group V-VI-VII ternary nanowires: moderate band gaps, easy to exfoliate from bulk, and unexpected ferroelectricity.

One-dimensional nanowires have emerged as compelling ideal materials due to their characteristic structure, properties, and applications in nanodevices. Herein, based on experimental vdW-chain bulk crystals, a series of one-dimensional (1D) XVYVIZVII (X = As, Sb, Bi; Y = S, Se, Te; Z = Cl, Br, I) ternary nanowires are theoretically investigated. Such exfoliated 1D nanowires possess excellent stability and moderate band gaps (1.76-3.16 eV). The calculated electron mobilities were found to reach a magnitude of 102 cm2 V-1 s-1 and even up to 322.95 cm2 V-1 s-1 for 1D BiSeI nanowires, which are much larger than those of the previously reported 1D materials. Furthermore, the appropriate band edge alignments and considerable optical absorption endow 1D XVYVIZVII nanowires with prospective photocatalytic properties for water splitting. Notably, AsSI and AsSeI nanowires possess a unique non-centrosymmetric structure and exhibit promising 1D ferroelectricity. Large spontaneous polarization values, Ps, of 11.31 × 10-10 and 6.92 × 10-10 C m-1 are obtained for 1D AsSI and AsSeI nanowires, respectively, and such 1D ferroelectricity can be regulated by intra-chain strains. Our calculations not only broaden the family of 1D materials but also reveal their great potential applications in electronic, optoelectronic, and ferroelectric devices.

Magnetic-field-regulated Ni-Fe-Mo ternary alloy electrocatalysts with enduring spin polarization enhanced oxygen evolution reaction

The oxygen evolution reaction (OER) constrains the efficiency of water splitting. The catalytic activity of electrocatalysts is mostly determined by the electronic structure, which is expressed as the electron transfer property and the reactant adsorption–desorption capacity. Ferromagnetic electrocatalysts exhibit promising applications in OER. However, an external magnetic field is indispensable for the electron spin polarization of ferromagnetic materials. Here, Ni-Fe-Mo ternary alloy nanowire electrocatalysts were prepared via a magnetic field-assisted self-assembly method in an aqueous-solution system at a mild temperature (65 °C). These Ni-Fe-Mo ternary alloy electrodes feature a spin polarization-dependent OER catalytic performance, which is attributed to ferromagnetic regulation. Ni0.8Fe0.15Mo0.05 possesses the maximum ferromagnetism compared to other electrodes (Ni0.8Mo0.2 and Ni0.8Fe0.2) and improved substantially OER activity. The regulated OER activity is assigned to the favorable adsorption of oxygen-containing intermediates (OH*) due to Ni-Fe-Mo composition-dependent, and the accelerated kinetics of OER with enduring spin polarization. The Ni-Fe-Mo ternary alloy nanowires with higher magnetic properties contribute to in situ spin polarization at the surface. This magnetic field-assisted synthesis approach provides a new strategy to realize electrodes with enduring spin polarized.

Monte Carlo study of the phase diagrams and hysteresis behaviors of a ternary mixed spin-(1, 1/2, 3/2) Ising nanowire with ferromagnetic core/ferrimagnetic shell structure

The hysteresis properties and phase diagrams of a ternary nanowire, composed of a ferromagnetic (FM) core of spin-1 encircled by a ferrimagnetic (FiM) shell of mixed spin-(1/2, 3/2). Monte Carlo simulation is used to study the effects of the exchange interactions (Rs, R1, R2 and RIF) and crystal fields (Dc, Ds) on the phase diagrams for various thicknesses of core and shell of the system. Our outcomes indicate that the compensation temperature exists for a particular range when Dc and Ds are present. In addition, a first and a second order phase transitions appear for different values of Dc, while a second phase transition appears for various values of Ds. Moreover, the hysteresis loops, coercivities and remanences of the system and three sublattices are discussed in detail. Multiple hysteresis loops such as double, triple and quintuple loops were found in the system for a various physical parameters. By comparing our findings to those of previous theoretical and experimental studies, a qualitative agreement can be found.