Electroplating and magnetostructural characterization of multisegmented Co54Ni46/Co85Ni15 nanowires from single electrochemical bath in anodic alumina templates
© Prida et al.; licensee Springer. 2013
Received: 16 November 2012
Accepted: 1 May 2013
Published: 4 June 2013
Highly hexagonally ordered hard anodic aluminum oxide membranes, which have been modified by a thin cover layer of SiO2 deposited by atomic layer deposition method, were used as templates for the synthesis of electrodeposited magnetic Co-Ni nanowire arrays having diameters of around 180 to 200 nm and made of tens of segments with alternating compositions of Co54Ni46 and Co85Ni15. Each Co-Ni single segment has a mean length of around 290 nm for the Co54Ni46 alloy, whereas the length of the Co85Ni15 segments was around 430 nm. The composition and crystalline structure of each Co-Ni nanowire segment were determined by transmission electron microscopy and selected area electron diffraction techniques. The employed single-bath electrochemical nanowire growth method allows for tuning both the composition and crystalline structure of each individual Co-Ni segment. The room temperature magnetic behavior of the multisegmented Co-Ni nanowire arrays is also studied and correlated with their structural and morphological properties.
KeywordsNanoporous alumina templates Electrodeposition Multisegmented nanowires 61.46.-w 68.37.Ma 75.75.-c
Research on nanostructures is motivated by the observation that material properties can abruptly change when scaling down the material size to nanoscale from its bulk counterpart mainly due to the enhanced surface-to-volume ratio of nanomaterials . Several techniques have been reported for the synthesis of materials at nanoscale [2, 3], but among these, the template-based method is a very simple and facile approach for obtaining dense metallic arrays with different geometries considered, such as planar and cylindrical nanostructures . Chemical template-based methods combined with high-yield electrochemical deposition techniques have been recently employed to synthesize ordered arrays of magnetic nanowires and nanotubes [5, 6]. The synthesis of nanostructured materials by means of electrochemical deposition into the nanopores of anodic aluminum oxide (AAO) membranes has attracted during the last decades a huge scientific interest due to the outstanding features exhibited by these templates such as low cost, large self-ordering degree of nanopores, high reproducibility, and precise control over their morphological characteristics . These fabrication techniques based on combined bottom-up strategies allow fabricating magnetic nanoentities by electrochemically filling the AAO pores, and the amount of electrodeposited material can be easily controlled through the charge recorded during the nanowire growth. This makes possible the preparation of highly ordered nanostructures with specific dimensions and properties [8, 9]. The peculiar characteristics of hard anodic aluminum oxide (H-AAO) membranes, mainly the low processing time, large interpore distances, and a broad window of self-ordering conditions, have demonstrated at the same time to be advantageous for their use as templates in the fabrication of highly ordered nanowire arrays . The high nanoporous oxide growth rate achieved by means of hard anodization (HA) method (about 50 μm/h, 20 times faster than the standard mild anodization), together with the fast development of a hexagonal highly ordered nanoporous arrangement, allows us to produce H-AAO membranes with reproducible geometrical parameters in a few hours by only performing a single anodization step .
Increasing interest has been focused on the study of ferromagnetic/non-magnetic heterogeneous nanowire arrays [12, 13], while only few works are devoted to heterogeneous ferromagnetic binary and segmented (barcode) nanowires [14, 15]. Co-Ni alloy nanowires are outstanding magnetic materials that can exhibit both either a soft or hard magnetic behavior depending on the Co/Ni ratio in the alloy [16–18]. The combination of low magnetocrystalline anisotropy of face-centered cubic (fcc) Ni and high magnetocrystalline anisotropy of hexagonal close-packed (hcp) Co, together with the high solubility of Co atoms in the crystalline lattice of Ni and vice versa for a wide range of relative concentrations , allows for the design of a material composition with tunable magnetic properties. The effective magnetic anisotropy energy is determined by the competition between the shape and magnetocrystalline anisotropies, together with the magnetostatic dipolar interactions among nanowires, being possible to tune the easy magnetization direction of the system between the longitudinal and perpendicular directions with respect to the nanowire axis [19, 20]. Additionally, the study on multisegmented magnetic nanowires, comprising alternate single segments of soft and hard magnetic materials with well-controlled thicknesses and separated by non-magnetic interspacers, has recently drawn the interest of the scientific community due to the interesting magnetization reversal processes that take place in these nanostructured materials that may allow for the design of multistable magnetic systems that are capable of storing several bits of information in a single nanowire . Consequently, the design and fabrication of multisegmented magnetic nanowire arrays with an accurate control of the crystalline structure and magnetocrystalline anisotropy of each nanowire segment plays a key role in the design of nanostructured magnetic materials with a required magnetic behavior for tailoring the magnetic and magnetotransport performance of nanostructured systems and devices .
In the present work, highly hexagonally ordered H-AAO membranes, which have been modified by a thin cover layer of SiO2 deposited by atomic layer deposition (ALD) method, were used as templates for the synthesis of electrodeposited multisegmented Co54Ni46/Co85Ni15 nanowire arrays with a diameter ranging between 180 and 200 nm and the length of each individual Co-Ni segment depending on its particular composition (around 290 nm for the Co54Ni46 segments, while around 430 nm for the Co85Ni15 ones). The optimum synthesis conditions for obtaining such multisegmented nanowires were established by carefully studying the electroplating of homogeneous Co-Ni alloy nanowire arrays grown at several electrochemical deposition potentials in order to determine the deposition rate and chemical composition of the deposits grown at each electrodeposition potential.
The composition and crystalline structure of each segment of the Co54Ni46/Co85Ni15 nanowires were determined by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), and selected area electron diffraction (SAED) techniques. The results indicate that our electrochemical growth method allows for tuning both the composition and crystalline structure of each individual Co-Ni segment deposited from a single electrolyte. The room temperature (RT) magnetic behavior of the multisegmented Co-Ni nanowire arrays has been also studied and correlated with their structural and morphological properties.
High-purity aluminum foils (Al 99.999%, Goodfellow, Coraopolis, PA, USA) were firstly cleaned by means of ultrasonication in isopropanol and ethanol for 5 min. Afterwards, the Al foils were placed into the anodization cell and electropolished up to a mirror-like finishing in a vigorously stirred mixture of perchloric acid and ethanol (25:75 vol.%) at 5°C, with an applied voltage of 20 V measured versus a Pt counter electrode. The Al substrates were then pre-anodized under mild anodization conditions at 80 V for 10 min in a 0.3 M oxalic acid aqueous solution containing 5 vol.% of ethanol at a temperature between 0°C and 3°C. Afterwards, the anodization voltage was increased at 0.08 V s−1 to reach potentiostatic conditions in the HA process, which was carried out at 140 V for 1.5 h. After the HA process, H-AAO membranes were released from the unoxidized Al substrate, which was removed by wet chemical etching in a CuCl2/HCl aqueous solution, and the membranes were subsequently immersed for 2.5 h in 5 wt.% H3PO4 at 30°C in order to remove the alumina barrier layer at the bottom of the pores, also increasing the pore size of the H-AAO membranes. This last chemical etching step also results in a complete dissolution of the protective mild anodization AAO layer on the top of the H-AAO membranes due to its lower chemical resistance to phosphoric acid etching compared to the H-AAO layer. Thus, the pores of the resulting H-AAO membrane are fully opened at both sides. Afterwards, the membranes were coated with a protective SiO2 conformal layer of 2 nm in thickness, deposited by ALD at 150°C from aminopropyltriethoxysilane (100°C), water (RT), and ozone (RT) that were employed as precursors and oxidant agent, respectively [23, 24]. The back side of the H-AAO templates was coated by means of sputtering and further electrodeposition of a continuous gold layer, which serves as a working electrode in the subsequent electrodeposition process of multisegments of Co-Ni alloy. Multisegmented Co54Ni46/Co85Ni15 nanowire arrays were electrochemically grown from a Watts-type bath containing 0.36 M CoSO4, 0.04 M CoCl2, 0.76 M NiSO4, 0.13 M NiCl2, and 0.73 M H3BO3. The pH of the electrolyte was adjusted to a value of 4 to 4.2 by adding 1 M NaOH. Electrodeposition processes were carried out at 35°C under potentiostatic conditions in a three-electrode electrochemical cell equipped with a Ag/AgCl reference electrode with a 3 M KCl, an insoluble Pt mesh counter electrode, and the gold-coated H-AAO template acting as the working electrode. The composition of each individual segment of the multisegmented Co54Ni46/Co85Ni15 nanowire arrays was tuned by adjusting the deposition potential in the range between −0.8 and −1.4 V versus the reference electrode. The duration of the potentiostatic deposition pulses was adjusted accordingly with the estimated deposition rate at each potential in order to obtain longitudinal segments of around 300 to 400 nm in length for each Co-Ni single segment. After the Co-Ni electrodeposition process, gold caps of about 2 μm in length were deposited in the upper part of the nanowires for protecting them from corrosion.
In order to perform a TEM characterization of individual multisegmented Co54Ni46/Co85Ni15 nanowires, it has been necessary to release them from the H-AAO template via chemical etching procedure. Firstly, the gold layer was partially removed by wet chemical etching in KI 0.6 M and I2 0.1 M aqueous solution, and the SiO2 protective coating covering the empty parts of the H-AAO template was removed by dipping the sample in diluted HF. Afterwards, the alumina membrane, which contains embedded nanowire arrays, was immersed in a mixture of H3PO4 (6 wt.%) and CrO3 (1.8 wt.%) at 45°C for 48 h, resulting in the total dissolution of the alumina template. Free-standing nanowires, protected by a thin SiO2 coating layer and gold caps at both ends of the nanowires, were then filtered and suspended in absolute ethanol. Then, a small amount of nanowires was dispersed in ethanol-distilled water mixture (1:1). Subsequently, the obtained suspension was sonicated for 30 min at RT. Finally, a drop of the dispersed solution was placed in a lacey carbon grid and dried for 30 min, and afterwards, the solvent was evaporated in ambient environment. TEM studies were carried out in a field emission gun microscope FEI Titan 80–300 kV (Hillsboro, OR, USA), operated at 300 kV. Scanning transmission electron microscopy (STEM) and TEM modes have been used to obtain the micrographs. The STEM mode images have been registered using the high-angle annular dark-field (HAADF)-STEM detector. The HAADF detector collects electrons diffracted at high angles, which are chemically sensitive. In addition, local elemental analyses of cobalt and nickel content were carried out by STEM coupled to the EDS technique along the long and short axes of a single nanowire (EDS line scan) in order to gain information about the composition of each nanowire segments. The microstructure of such segments was investigated by SAED measurements.
Additionally, scanning electron microscope (JEOL 6610-LV, Akishima, Tokyo, Japan), equipped with EDS, was also employed for the morphological and compositional characterization of both the H-AAO templates and homogenous Co-Ni nanowires in order to determine the optimal synthesis conditions for the deposition of multisegmented Co-Ni nanowires.
The RT magnetic behavior of the multisegmented Co-Ni nanowire arrays was studied by means of vibrating sample magnetometer (VSM, Versalab-Quantum Design, San Diego, CA, USA) under a maximum applied magnetic field of ±30 kOe along both parallel and perpendicular directions with respect to the nanowire longitudinal axes.
Results and discussion
It is worth to point out that the composition profiles obtained from the linear EDS scans of Figure 4b performed in the multisegmented Co-Ni nanowires by STEM mode do not fit to pulse function as the applied deposition potentials do, probably ascribed to relaxation effects that occur during the deposition processes.
The local examination of the microstructure and composition of the different nanowire segments revealed that their crystalline structure changes as the Co/Ni ratio is modified. Particularly, it was found that nanowire segments containing at least 60% of cobalt display SAED patterns which correspond to hcp single crystals grown along the <10-10 > direction. On the other hand, nanowire segments containing below 60% of cobalt exhibit SAED patterns corresponding to a Co-Ni alloy single crystal with a fcc structure, where the <111 > direction lies along the nanowire axis. Representative examples are shown in Figure 5. In particular, the segment highlighted with number (1) on the left of Figure 5 has a composition of Co83Ni17, which was determined by EDS operating the microscope in TEM mode. The spots of the corresponding SAED pattern can be indexed to the  zone axis of a Co-Ni single crystal with hcp structure. In addition, it is observed that the <10-10 > direction lies along the nanowire axis. On the other hand, the segment highlighted with number (2) having Co52Ni48 composition exhibits a SAED pattern that can be indexed to the [−321] zone axis of a Co-Ni alloy with fcc structure, where the <111 > direction lies along the nanowire axis. Interestingly, in several of these SAED patterns, the diffraction spots appear slightly elongated, or well, two or three spots appear very close. This fact evidences a texture that could be originated by fluctuations in the distribution of the Co/Ni ratio into the same segment and/or the effect of transversal stresses produced by the confined growth into the pores of the alumina template. The appearance of the hcp structure for Co-Ni alloys with high Co content is in agreement with its equilibrium phase diagram . However, it is worth noting that in some of the studied nanowire segments, the concentration fluctuations and structural differences have also appeared, probably as a consequence of the non-equilibrium nature of the electrodeposition processes.
ALD SiO2-coated multisegmented Co85Ni15/Co54Ni46 nanowire arrays, with around 180 nm in diameter and made of tens of alternating segments with respective compositions of Co54Ni46 and Co85Ni15 having several hundreds of nanometers in length (around 290 nm for the segments of Co54Ni46 alloy and around 430 nm for the Co85Ni15 segments), have been synthesized by template-assisted electrochemical deposition into the pores of H-AAO templates by alternately varying between two different deposition potentials. Both Co content and nanowire growth rate vary quasi-linearly with the deposition potential. Based on this relation, the desired Co-Ni composition in each individual segment can be simply controlled by properly choosing the deposition potential. SAED allows distinguishing between the structures of both nanowire segments, being hcp for the Co85Ni15 segment, while fcc for the Co54Ni46 one, due to the influence of higher presence of fcc Ni in the alloy rather than changes induced during the electrodeposition dynamics. This technique allows not only for tuning the composition of the nanowires but also their crystalline structure in each different nanowire segments, which also affects the magnetic behavior making this system magnetically isotropic.
The financial support from EU-Nanomagma under FP7-214107-2, LEXI-Spintronic funded by the State of Hamburg and Spanish MICINN under research projects MAT2009-13108-C02-01 and MAT2010-20798-C05-04 is acknowledged. The partial support from the Mexican Council of Science and Technology (CONACYT) and Universidad Autónoma de Nuevo León under research projects CB-179486 and PAICYT-CE793-11 is also acknowledged. Victor Vega is grateful to the German Academic Exchange Service (DAAD) and University of Oviedo for the grants supporting his internships. Javier García thanks FICyT for his Severo Ochoa fellowship. Scientific support from the University of Oviedo SCT is also recognized.
- Arico AS, Bruce P, Scrosati B, Tarascon J-M, van Schalkwijk W: Nanostructured materials for advanced energy conversion and storage devices. Nature Mater 2005, 4: 366–377.View ArticleGoogle Scholar
- Rao CNR, Deepak FL, Gundiah G, Govindaraj A: Inorganic nanowires. Progress in Solid State Chemistry 2003, 31: 5–147. 10.1016/j.progsolidstchem.2003.08.001View ArticleGoogle Scholar
- Rao CNR, Govindaraj A: Synthesis of inorganic nanotubes. Adv Mater 2009, 21: 4208–4233. 10.1002/adma.200803720View ArticleGoogle Scholar
- Hangarter CM, Lee Y-I, Hernandez SC, Y-h C, Myung NV: Nanopeapods by galvanic displacement reaction. Angew Chem Int Ed 2010, 49: 7081–7085. 10.1002/anie.201001559View ArticleGoogle Scholar
- Li X, Wang Y, Song G, Peng Z, Yu Y, She X, Li J: Synthesis and growth mechanism of Ni nanotubes and nanowires. Nanoscale Res Lett 2009, 4: 1015–1020. 10.1007/s11671-009-9348-0View ArticleGoogle Scholar
- Proenca MP, Sousa CT, Ventura J, Vazquez M, Araujo JP: Distinguishing nanowire and nanotube formation by the deposition current transients. Nanoscale Res Lett 2012, 7: 280. 10.1186/1556-276X-7-280View ArticleGoogle Scholar
- Masuda H, Fukuda K: Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina. Science 1995, 268: 1466–1468. 10.1126/science.268.5216.1466View ArticleGoogle Scholar
- Nielsch K, Müller F, Li A-P, Gösele U: Uniform nickel deposition into ordered alumina pores by pulsed electrodeposition. Adv Mater 2000, 12: 582–586. 10.1002/(SICI)1521-4095(200004)12:8<582::AID-ADMA582>3.0.CO;2-3View ArticleGoogle Scholar
- Vázquez M, Pirota K, Hernández-Vélez M, Prida VM, Navas D, Sanz R, Batallán F, Velázquez J: Magnetic properties of densely packed arrays of Ni nanowires as a function of their diameter and lattice parameter. J Appl Phys 2004, 95: 6642. 10.1063/1.1687539View ArticleGoogle Scholar
- Vega V, Böhnert T, Martens S, Waleczek M, Montero-Moreno JM, Görlitz D, Prida VM, Nielsch K: Tuning the magnetic anisotropy of Co-Ni nanowires: comparison between single nanowires and nanowire arrays in hard-anodic aluminum oxide membranes. Nanotechnology 2012, 23: 465709. 10.1088/0957-4484/23/46/465709View ArticleGoogle Scholar
- Lee W, Ji R, Gösele U, Nielsch K: Fast fabrication of long-range ordered porous alumina membranes by hard anodization. Nature Mater 2006, 5: 741–747.View ArticleGoogle Scholar
- Tang X-T, Wang G-C, Shima M: Magnetic layer thickness dependence of magnetization reversal in electrodeposited CoNi/Cu multilayer nanowires. J Magn Magn Mater 2007, 309: 188–196. 10.1016/j.jmmm.2006.06.032View ArticleGoogle Scholar
- Shakya P, Cox B, Davis D: Giant magnetoresistance and coercivity of electrodeposited multilayered FeCoNi/Cu and CrFeCoNi/Cu. J Magn Magn Mater 2012, 324: 453–459. 10.1016/j.jmmm.2011.08.023View ArticleGoogle Scholar
- Clime L, Zhao SY, Chen P, Normandin F, Roberge H, Veres T: The interaction field in arrays of ferromagnetic barcode nanowires. Nanotechnology 2007, 18: 435709. 10.1088/0957-4484/18/43/435709View ArticleGoogle Scholar
- Maijenburg AW, George A, Samal D, Nijland M, Besselink R, Kuiper B, Kleibeuker JE, ten Elshof JE: Electrodeposition of micropatterned NiPt multilayers and segmented NiPtNi nanowires. Electrochim Acta 2012, 81: 123–128.View ArticleGoogle Scholar
- Talapatra S, Tang X, Padi M, Kim T, Vajtai R, Sastry GVS, Shma M, Deevi SC, Ajayan PM: Synthesis and characterization of cobalt–nickel alloy nanowires. J Mater Sci 2009, 44: 2271–2275. 10.1007/s10853-008-3015-1View ArticleGoogle Scholar
- Vivas LG, Vázquez M, Vega V, García J, Rosa WO, del Real RP, Prida VM: Temperature dependent magnetization in Co-base nanowire arrays: role of crystalline anisotropy. J Appl Phys 2012, 111: 07A325. 10.1063/1.3676431View ArticleGoogle Scholar
- Vivas LG, Vázquez M, Escrig J, Allende S, Altbir D, Leitao DC, Araujo JP: Magnetic anisotropy in CoNi nanowire arrays: analytical calculations and experiments. Phys Rev B 2012, 85: 035439.View ArticleGoogle Scholar
- Vega V, Prida VM, García JA, Vázquez M: Torque magnetometry analysis of magnetic anisotropy distribution in Ni nanowire arrays. Physica Status Solidi A 2011, 208: 553–558. 10.1002/pssa.201026390View ArticleGoogle Scholar
- Pirota KR, Béron F, Zanchet D, Rocha TCR, Navas D, Torrejón J, Vázquez M, Knobel M: Magnetic and structural properties of fcc/hcp bi-crystalline multilayer Co nanowire arrays prepared by controlled electroplating. J Appl Phys 2011, 109: 083919. 10.1063/1.3553865View ArticleGoogle Scholar
- Allende S, Vargas NM, Altbir D, Vega V, Görlitz D, Nielsch K: Magnetization reversal in multisegmented nanowires: parallel and serial reversal modes. Appl Phys Lett 2012, 101: 122412. 10.1063/1.4754117View ArticleGoogle Scholar
- Rheem Y, Yoo B-Y, Beyermann WP, Myung NV: Electro- and magneto-transport properties of a single CoNi nanowire. Nanotechnology 2007, 18: 125204. 10.1088/0957-4484/18/12/125204View ArticleGoogle Scholar
- Knez M, Nielsch K, Niinistö L: Synthesis and surface engineering of complex nanostructures by atomic layer deposition. Adv Mater 2007, 19: 3425–3438. 10.1002/adma.200700079View ArticleGoogle Scholar
- Bachmann J, Zierold R, Chong YT, Hauert R, Sturm C, Schmidt-Grund R, Rheinländer B, Grundmann M, Gösele U, Nielsch K: A practical, self-catalytic, atomic layer deposition of silicon dioxide. Angew Chem Int Ed 2008, 47: 6177–6179. 10.1002/anie.200800245View ArticleGoogle Scholar
- Srivastava M, Selvi VE, Grips VKW, Rajam KS: Corrosion resistance and microstructure of electrodeposited nickel–cobalt alloy coatings. Surf Coat Tech 2006, 201: 3051–3060. 10.1016/j.surfcoat.2006.06.017View ArticleGoogle Scholar
- Hansen M: Constitution of Binary Alloys. 2nd edition. New York: McGraw-Hill; 1958:486.Google Scholar
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