Cobalt Nanowire Arrays Research Articles

Review of: "Magnetic nanowires such as cobalt, nickel, iron and alloys can be made by electroaccumulation and spontaneous accumulation on an anodic aluminum oxide mold, and the magnetic properties of cobalt nanowire arrays such as coercive force"

Review of: "Magnetic nanowires such as cobalt, nickel, iron and alloys can be made by electroaccumulation and spontaneous accumulation on an anodic aluminum oxide mold, and the magnetic properties of cobalt nanowire arrays such as coercive force"

High-Coercivity Cobalt Nanowire Arrays: Synthesis and Heat Treatment

High-Coercivity Cobalt Nanowire Arrays: Synthesis and Heat Treatment

Crystalline texture of cobalt nanowire arrays probed by the switching field distribution and FORC diagrams

The crystalline texture of arrays of low diameter Co nanowires (NWs) synthesized by electrodeposition using electrolytes with different acidities (pH in the range 2.0–6.6) was studied by the switching field distribution (SFD) and first order reversal curve (FORC) diagrams. Particularly, the SFD determined as the derivative of the descending part of the major hysteresis loop has proven to be a reliable and powerful method for the identification of different crystalline textures in the NWs and the quantification of their corresponding texture percentages. The presence of the face centered cubic-like texture at low pH values and hexagonal close packed textures with the c-axis perpendicular and parallel to the NWs axis at higher pH values have been identified by performing multiple Gaussian fits to the SFD by virtue of their different magnetic behavior observed during reversal of the magnetization. The field position and size of each curve in the multiple Gaussian fit provide information about the corresponding magnetic contribution and volumetric texture percentage of each crystalline texture in the NWs, respectively. The analysis of the SFD has been complemented and validated with FORC diagram measurements, showing that the width of the coercive field distribution is in good agreement with the width of the SFD. Also, it has been found that the different branches observed in the FORC diagrams along the interaction axis provide further insight on the interaction between magnetocrystalline fields. This work provides a novel methodology for the use of magnetometry as a reliable technique for the study of the interplay between the microstructure and magnetic behavior of arrays of NWs.

Bragg-type Brillouin spectroscopy of spin waves on ultrathin nickel nanowires

We study the optical and magneto-optical properties of low-concentration arrays of ultrathin nickel nanowires by means of Brillouin spectroscopy of thermal magnons. Brillouin spectroscopy in such quasitransparent magneto-optical structures is dominated by the Bragg phase synchronism mechanism. At variance with ultrathin cobalt nanowire arrays, the Stokes/anti-Stokes scattering pattern is practically symmetrical. This feature is attributed to their peculiar optical properties.

Determination of cathode current efficiency for electrodeposition of ferromagnetic cobalt nanowire arrays in nanochannels with extremely large aspect ratio

Cathode current efficiency for the electrodeposition of cobalt from an acidic aqueous solution, which took place in anodized aluminum oxide (AAO) nanochannels with an average diameter of ca. 25 nm, was determined by Faraday’s first law of electrolysis. The electrodeposited metallic cobalt crystals were grown as an array of nanowires embedded in the nanochannels. The amount of charge consumed for the electrochemical reduction in the nanochannels was estimated considering the time dependence of the cathode current during the electrodeposition of the cobalt nanowires. Meanwhile, the volume of electrodeposition on the cobalt nanowires was determined from the saturated magnetic moment of the nanowires, which was obtained from the magnetization curves. The cathode current efficiency for the electrodeposition of the cobalt nanowire arrays remained at a high level (over 75%) in the cathode potential ranging from −0.70 V to −0.85 V vs. Ag/AgCl. At the cathode potential of −0.80 V, the cathode current efficiency reached 97%. The texture coefficient TC(0 0 2) of the cobalt nanowire arrays increased as the cathodic overpotential for the electrodeposition of cobalt decreased. Due to the extremely large aspect ratio (more than 1000), the cobalt nanowire arrays were spontaneously magnetized in the direction parallel to the long axis of the nanowires. With increasing TC(0 0 2), the coercivity and squareness of the cobalt nanowire arrays also increased up to ca. 1.6 kOe and 0.8, respectively, at room temperature.

Determination of Crystal Growth Geometry Factors and Nucleation Site Densities of Electrodeposited Ferromagnetic Cobalt Nanowire Arrays

The time-dependence of electrochemical reduction current, which was observed during the one-dimensional (1-D) crystal growth of ferromagnetic cobalt nanowire arrays, was analyzed by Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory. Textured hcp-Co nanowire arrays were synthesized by potentio-static electrochemical reduction of Co2+ ions in anodized aluminum oxide (AAO) nanochannel films. Crystal growth geometry factor n in the JMAK equation was determined to be ca. 1. Hence, the electrochemical crystal growth process of a numerical nanowires array can be explained by 1-D geometry. The crystal nucleation frequency factor, k in JMAK equation was estimated to be the range between 10−4 and 10−3. Our experimental results revealed that the crystal nucleation site density Nd increased up to 2.7 × 10−8 nm−3 when increasing the overpotential for cobalt electrodeposition by shifting the cathode potential down to −0.85 V vs. Ag/AgCl. The (002) crystal orientation of hcp-Co nanowire arrays was, remarkably, observed by decreasing Nd. Spontaneous magnetization behavior was observed in the axial direction of nanowires. By decreasing the overpotential for cobalt electrodeposition, the coercivity of the nanocomposite film increased and reached up to 1.88 kOe, with a squareness of ca. 0.9 at room temperature.

Flipping anisotropy and changing magnetization reversal modes in nano-confined Cobalt structures

Abstract We investigate the temperature dependent magnetic properties of arrays of Cobalt nanowires created by sputtering Co on two separate nanoporous anodized alumina (AAO) templates each with pores of diameter 50 nm and 10 nm. We observe differences in the easy axis of magnetization for the two nanowire arrays and a flip in the easy axis at low temperatures. The easy axis of 50 nm nanowire array at room temperature is found to be perpendicular to the nanowire long axis, whereas for 10 nm arrays the easy axis is parallel to the wire axis. With lowering of temperature, however the easy axes of both arrays orient away from that at room temperature. Along with that the saturation magnetic field and coercive field show sudden increase in their values at low temperatures, accompanied by a crossing over seen in the saturation magnetic fields. We propose changes in magneto-crystalline anisotropy of cobalt present in the nanowires as a result of the stress developed in the nanowire array due to the alumina template, with lowering of temperature. We support our experimental results with micro-magnetic simulations done to generate the M(H) curves and study the magnetization reversal processes in the nanowire arrays with varying anisotropies. With lowering of anisotropy which we believe is triggered by stress at low temperature, our simulations show magnetic vortex like instabilities originating in the nanowires. We suggest the possible modes of domain reversals: curling in 50 nm and either coherent rotation or buckling in 10 nm nanowires through our simulations. Our results suggest that temperature can serve as an effective tool to tune magnetic anisotropy in Co nanowires embedded in AAO and generate unusual magnetic textures.

Determination of Activation Overpotential during the Nucleation of Hcp-Cobalt Nanowires Synthesized by Potentio-Static Electrochemical Reduction.

The crystal growth process and ferromagnetic properties of electrodeposited cobalt nanowires were investigated by controlling the bath temperature and cathodic overpotential. The cathodic overpotential during electrodeposition of cobalt nanowire arrays, ΔEcath, was theoretically estimated by the difference between the cathode potential, Ecath, and the equilibrium potential, Eeq, calculated by the Nernst equation. On the other hand, the activation overpotential, ΔEact, was experimentally determined by the Arrhenius plot on the growth rate of cobalt nanowire arrays, Rg, versus (vs.) reciprocal temperature, 1/T. The ferromagnetic cobalt nanowire arrays with a diameter of circa (ca.) 25 nm had the preferred crystal orientation of (100) and the aspect ratio reached up to ca. 1800. The average crystal grain size, Ds, of (100) peaks was estimated by X-ray diffraction patterns and was increased by decreasing the cathodic overpotential for cobalt electrodeposition by shifting the cathode potential in the noble direction. Axial magnetization performance was observed in the cobalt nanowire arrays. With increasing Ds, coercivity of the film increased and reached up to ca. 1.88 kOe.

A versatile electrochemical method to synthesize Co-CoO core-shell nanowires anodes for lithium ion batteries with superior stability and rate capability

A novel electrochemical method is proposed to synthesize nanostructured cobalt electrodes for lithium-ion batteries (LIBs). An array of cobalt nanowires (CoNWs) supported by a nanostructured copper current collector was obtained by the sequential electrodeposition of cobalt and copper into the nanopores of alumina templates and selective etching of alumina. The illustrated method can be implemented with one-side open alumina templates generated by one-step aluminium anodization, thus excluding the application alumina membranes and their coating by sputter metal deposition. The cobalt electrodeposition conditions allow to directly form Co-CoO core-shell nanowires, with metallic cobalt nanowires covered by a thin cobalt oxide film. The direct electrochemical growth of copper nanowires connected to CoNWs ensured high electronic conductivity and specific surface area of the resulting electrode, leading to a low interfacial impedance when used in lithium cell. This nanostructure and the enhanced lithium diffusion enabled by the nanowires morphology contributed to achieve a specific capacity of 1500 mAhg−1 after 200 cycles at 2 Ag-1, and complete restore of the capacity at 2 Ag-1 after cycling at the ultra-high current density of 450 Ag-1. The faradaic and capacitive contributions to charge storage were estimated by the analysis of cyclic voltammetry experiments carried out at different scan rates. Based on this latter analysis, pseudo-capacitive effects appear to play a pivotal role in determining the total recorded capacity. The advantages of the proposed method to sustain the large scale application of nanowires electrodes in lithium batteries are thoroughly discussed.

Domain wall structure and interactions in 50 nm wide Cobalt nanowires

Arrays of cobalt nanowires with widths of 50 nm, thickness of 5 and 20 nm and periodicity of 70 nm were fabricated by pattern transfer from a self-assembled block copolymer film. Transverse domain walls (DWs) were imaged by magnetic force microscopy, indicating repulsive interactions between DWs of the same sign in the 20 nm thick wires. Micromagnetic simulations were used to identify the interactions in the six distinct cases of a pair of transverse DWs in adjacent wires, considering all the possible combinations of head-to-head and tail-to-tail DWs and the orientation of the core magnetization. The boundary between repulsive and attractive DW interactions is mapped out for wires as a function of thickness, width and interwire spacing.

An ultrafine platinum–cobalt alloy decorated cobalt nanowire array with superb activity toward alkaline hydrogen evolution

It is highly desired to design and develop highly efficient electrocatalysts for alkaline hydrogen evolution reactions. Herein, we report the development of ultrafine PtCo alloy nanoparticle decorated one-dimensional Co nanowires grown on Ti mesh (PtCo-Co/TiM). Owing to its favorable composition and structure, the PtCo-Co/TiM can deliver an ultrahigh current density of 46.5 mA cm-2 at an overpotential of 70 mV in 1.0 M KOH, superior to recently reported Pt-based electrocatalysts. This catalyst also provides excellent long-term electrochemical durability with its catalytic activity being maintained for at least 50 h.

Morphology, directed self-assembly and pattern transfer from a high molecular weight polystyrene-block-poly(dimethylsiloxane) block copolymer film

The self-assembly of block copolymers with large feature sizes is inherently challenging as the large kinetic barrier arising from chain entanglement of high molecular weight (MW) polymers limits the extent over which long-range ordered microdomains can be achieved. Here, we illustrate the evolution of thin film morphology from a diblock copolymer of polystyrene-block-poly(dimethylsiloxane) exhibiting total number average MW of 123 kg mol−1, and demonstrate the formation of layers of well-ordered cylindrical microdomains under appropriate conditions of binary solvent mix ratio, commensurate film thickness, and solvent vapor annealing time. Directed self-assembly of the block copolymer within lithographically patterned trenches occurs with alignment of cylinders parallel to the sidewalls. Fabrication of ordered cobalt nanowire arrays by pattern transfer was also implemented, and their magnetic properties and domain wall behavior were characterized.

Enhanced magnetocrystalline anisotropy in an ultra-dense array of air-exposed crystalline cobalt nanowires

The magnetic anisotropy of an ultradense array of crystalline cobalt nanowires is investigated by means of broadband ferromagnetic resonance and magnetic torque measurements. The array is grown epitaxially in solution on a Pt(111) film and consists of single crystalline metallic wires with a diameter of 6.2 nm and a center-to-center interwire distance of 9.6 nm. The shape anisotropy and the Co hexagonal compact structure with the c-axis along the wire axis combine with each other to impose a perpendicular magnetic anisotropy despite the high density of 8 × 1012 wires/in.2. The intrinsic uniaxial magnetocrystalline anisotropy constants K1 and K2 are extracted from the ferromagnetic resonance and torque measurements using a mean field approach accounting for the interwire dipolar interactions. At room temperature, and despite air exposure, an unexpected increase of K1 and K2 of more than 40% with respect to the bulk is evidenced.

Developing high coercivity in large diameter cobalt nanowire arrays

Regardless of the synthetic method, developing high magnetic coercivity in ferromagnetic nanowires (NWs) with large diameters has been a challenge over the past two decades. Here, we report on the synthesis of highly coercive cobalt NW arrays with diameters of 65 and 80 nm, which are embedded in porous anodic alumina templates with high-aspect-ratio pores. Using a modified electrochemical deposition method enabled us to reach room temperature coercivity and remanent ratio up to 3000 Oe and 0.70, respectively, for highly crystalline as-synthesized hcp cobalt NW arrays with a length of 8 μm. The first-order reversal curve (FORC) analysis showed the presence of both soft and hard magnetic phases along the length of the resulting NWs. To develop higher coercive fields, the length of the NWs was then gradually reduced in order from bottom to top, thereby reaching NW sections governed by the hard phase. Consequently, this resulted in record high coercivities of 4200 and 3850 Oe at NW diameters of 65 and 80 nm, respectively. In this case, the FORC diagrams confirmed a significant reduction in interactions between the magnetic phases of the remaining sections of NWs. At this stage, x-ray diffraction (XRD) and dark-field transmission electron microscopy analyses indicated the formation of highly crystalline bamboo-like sections along the [0 0 2] direction during a progressive pulse-controlled electrochemical growth of NW arrays under optimized parameters. Our results both provide new insights into the growth process, crystalline characteristics and magnetic phases along the length of large diameter NW arrays and, furthermore, develop the performance of pure 3d transition magnetic NWs.

Single crystalline cylindrical nanowires - toward dense 3D arrays of magnetic vortices.

Magnetic vortex-based media have recently been proposed for several applications of nanotechnology; however, because lithography is typically used for their preparation, their low-cost, large-scale fabrication is a challenge. One solution may be to use arrays of densely packed cobalt nanowires that have been efficiently fabricated by electrodeposition. In this work, we present this type of nanoscale magnetic structures that can hold multiple stable magnetic vortex domains at remanence with different chiralities. The stable vortex state is observed in arrays of monocrystalline cobalt nanowires with diameters as small as 45 nm and lengths longer than 200 nm with vanishing magnetic cross talk between closely packed neighboring wires in the array. Lorentz microscopy, electron holography and magnetic force microscopy, supported by micromagnetic simulations, show that the structure of the vortex state can be adjusted by varying the aspect ratio of the nanowires. The data we present here introduce a route toward the concept of 3-dimensional vortex-based magnetic memories.

Tunable magnetocrystalline easy axis in cobalt nanowire arrays by zinc additive

Abstract A new approach to tuning the crystalline characteristics and magnetic properties of cobalt nanowire (NW) arrays embedded in AAO templates is reported using zinc additive. This is realized by adding low concentrations of Zn when pulse-electrodepositing cobalt NWs while also increasing the solution pH from 3 to 5. Using hysteresis loop measurements with a magnetic field applied parallel to the NW axis, coercivity and squareness of pure cobalt NWs increased from 890 Oe and 0.45 to 2150 Oe and 0.93 in Co 97 Zn 3 NWs, respectively, using a Zn concentration of 0.01 M at pH = 4. XRD patterns obtained from the cobalt-rich CoZn NWs revealed that the crystalline texture of cobalt changes from [1 0 0] direction to [1 0 1] and [0 0 2] at pH = 3 and 4, respectively. For the latter, the magnetocrystalline easy axis of cobalt rotates from nearly perpendicular to parallel to the NW axis, induced by the incorporation of zinc into the hcp structure of cobalt.

2D and 3D ordered arrays of Co magnetic nanowires

Cobalt nanowire arrays spatially distributed in 2D and 3D arrangements have been performed by pulsed electrodeposition into the pores of planar and cylindrical nanoporous anodic alumina membranes, respectively. Morphological characterization points out the good filling factor reached by electroplated Co nanowires in both kinds of alumina membranes exhibiting hexagonally self-ordered porous structures. Co nanowires grown in both kinds of alumina templates exhibit the same crystalline phases. DC magnetometry and First Order Reversal Curve (FORC) analysis were carried out in order to determine the overall magnetic behavior for both nanowire array geometries. It is found that when the Co nanowires of two kinds of arrays are perpendicularly magnetized, both hysteresis loops are identical, suggesting that neither the intrinsic magnetic behavior of the nanowires nor the collective one depend on the arrays geometry. FORC analysis performed along the radial direction of the Co nanowire arrays embedded in the cylindrical alumina template reveals that the contribution of each nanowire to the magnetization reversal process involves its specific orientation with respect to the applied field direction. Furthermore, the comparison between the magnetic properties for both kinds of Co nanowire arrays allows discussing about the effect of the cylindrical geometry of the template on the magnetostatic interaction among nanowires.

Ultrahigh-density sub-10 nm nanowire array formation via surface-controlled phase separation.

We present simple, self-assembled, and robust fabrication of ultrahigh density cobalt nanowire arrays. The binary Co-Al and Co-Si systems phase-separate during physical vapor deposition, resulting in Co nanowire arrays with average diameter as small as 4.9 nm and nanowire density on the order of 10(16)/m(2). The nanowire diameters were controlled by moderating the surface diffusivity, which affected the lateral diffusion lengths. High resolution transmission electron microscopy reveals that the Co nanowires formed in the face-centered cubic structure. Elemental mapping showed that in both systems the nanowires consisted of Co with undetectable Al or Si and that the matrix consisted of Al with no distinguishable Co in the Co-Al system and a mixture of Si and Co in the Co-Si system. Magnetic measurements clearly indicate anisotropic behavior consistent with shape anisotropy. The dynamics of nanowire growth, simulated using an Ising model, is consistent with the experimental phase and geometry of the nanowires.

A comparison of the magnetic properties of Ni and Co nanowires deposited in different templates and on different substrates

Nickel (Ni) and cobalt (Co) nanowire arrays (NWs) grown by electrodeposition in porous nano-templates are studied by the ferromagnetic resonance (FMR) technique at room temperature (RT) by comparing the effects of template type (alumina and polycarbonate) and the deposition substrate (i.e., metallic back contact). The line-width and resonance field of the FMR spectra strongly depends on the orientation of the applied field direction. A model is developed to analyze the spectra in order to extract the magnetic parameters such as g-values, spin–spin relaxation times (T2) and uniaxial anisotropy parameters. The experimental FMR spectra and their resonance field values were fitted using the imaginary part of magnetic susceptibility and a dispersion relation of magnetization, including the Bloch–Bloembergen type damping term. The easy axes of magnetization for all Ni and Co NWs were found to be perpendicular to the wire-axis. Surface spin modes have been observed only when pure Au was used as substrate. A discussion will be provided to explain the observed differences in terms of the anisotropic behavior and magnetic parameters of the NWs for different substrates and growth templates.

Interface coupling-induced enhancement of magnetoimpedance effect in heterogeneous nanobrush by adjusting textures of Co nanowires

Interface coupling-induced and interface coupling-enhanced magnetoimpedance (MI) effect in heterogeneous nanobrush has been investigated. The nanobrush is composed of Fe25Ni75 nanofilm and textured hexagonal close-packed cobalt nanowire array, respectively fabricated by RF magnetron sputtering and electrochemical deposition. The design of this structure is based on the vortex distribution of magnetic moments in thin film, which can be induced by the exchange coupling effect at the interfaces of the nanobrush. The texture of nanowires plays an important role in the MI effect of the nanobrush, which is regulated by controlling the pH values and temperatures of the deposition process. The ‘parallel’ and ‘perpendicular’ coupling models were used to explain the different MI results of the nanobrush with cobalt nanowires, which have (100) and (002) textures, respectively. The optimized MI effect of the nanobrush brought by (100) nanowires can be magnified by 300% with more than 80%/Oe magnetic sensitivity at a low frequency, which has great application potentials in low-frequency MI sensors.