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Journal of Spintronics and Magnetic Nanomaterials Vol. 1, 2327, 2012

AC Electrodeposition of Amorphous CoP Nanowires Embedded in an Alumina Template

F. Nasirpouri1 , S. M. Peighambari1 , S. J. Bending2 , E. V. Sukovatitsina3 , and A. S. Samardak3
Department of Materials Engineering, Sahand University of Technology, Tabriz 51335-1996, Iran 2 Department of Physics, University of Bath, Bath BA2 7AY, UK 3 Laboratory of Thin Film Technologies, School of Natural Sciences, Far Eastern Federal University, Vladivostok 690950, Russia In this paper we report on the fabrication of amorphous CoP alloy nanowires by means of alternating current (ac) electrodeposition in an highly ordered anodic aluminum oxide (AAO) template. An ac voltage with sinusoidal waveform at a xed frequency of 400 Hz was applied to electrodeposit nanowires from aqueous solutions with different phosphorous content at room temperDelivered by Ingenta to: ature. Current transients demonstrate the general four-stage nucleation and growth behavior of Sahand University of Technology nanowires in nanoporous templates and scanning electron microscopy conrms the formation of IP : 80.191.211.21 CoP nanowires in AAO. Results show that electrolyte phosphorous content inuences the growth, Thu, 27 18:40:51 microstructure and magnetic properties ofSep the 2012 nanowires. An increase of phosphorus content reduces the growth rate of nanowires. The crystalline structure of cobalt nanowires electrodeposited in AAO changes signicantly to amorphous by the incorporation of phosphorous as an alloying element in the structure, as X-ray diffraction patterns show. Furthermore, the coercivity of the CoP nanowires decreases when the electrolyte phosphorous content increases.
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Keywords: CoP, Nanowires, AAO, Electrodeposition, Amorphous.

RESEARCH ARTICLE

1. INTRODUCTION
The controlled production of magnetic nanowire arrays with outstanding characteristics is attracting much interest recently owing to their applications in emerging technologies related with magnetic information storage, high sensitivity GMR sensor devices, thermoelectric cooling system and photonic crystals.1 2 Patterning materials using templating is a very cheap and efcient synthesis technique. Templating is not an established technique for magnetic media at the microscale, but interest in using this technique is growing rapidly due to the ease of fabrication of materials in the nanoscale range in an efcient and cost effective way. There are several ways to ll the nanopores with metals or other materials to form nanowires, but the electrochemical deposition method is a general and versatile method which has been successfully used for creating nanowires of magnetic, semiconductor, and superconductor materials.35 Various templates have been used to electrodeposit nanowires, but the anodic aluminium oxide (AAO) template method has been applied widely due to its

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self-oraganized nanopore structure, convenience and exibility of fabrication.6 7 There are two main factors determining the magnetic properties of the nanowire arrays: (1) the magnetic character of individual nanowires, which is determined by its magnetic anisotropy, such as magnetocrystalline anisotropy and shape anisotropy, and (2) the periodicity or the symmetry of nanowire arrays, which determines the strength of the magnetostatic interaction between nanowires.8 If the microstructure is amorphous in nature, then the magnetocrystalline anisotropy can be neglected. Electrodeposition has been widely used for the synthesis of amorphous alloys including binary transitionmetalmetalloid glasses such as NiP, CoP, and FeP. The microstructure and magnetic properties of the materials depends on the composition, and can be controlled by varying the electrodeposition conditions such as the electrolyte and the current density.9 Arrays of amorphous NiP and CoP nanowires have been dc electrodeposited into polymeric and AAO templates. The microstructure and magnetic properties of the nanowire arrays were demonstrated to strongly depend upon the composition, i.e., content of phosphorous (%P) and could be controlled by varying the composition, pH and the temperature of the electrodeposition bath. It was implied that the replacement
2158-866X/2012/1/023/005 doi:10.1166/jsm.2012.1008

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AC Electrodeposition of Amorphous CoP Nanowires Embedded in an Alumina Template

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of Ni with Co results in both a decrease of the coercive eld and an increase of the Curie temperature.10 However, little research has been carried out on the ac electrodeposition of amorphous magnetic nanowires. More recently, CoP and FeCoP nanowires were synthesized in AAO by ac electrodeposition11 12 showing the existence of a relationship between bath composition, i.e., sodium hypophosphite concentration and the P content of nanowires, which were found to be amorphous in structure. The magnetic hysteresis loops showed the easy magnetizing axis is parallel to the nanowires, suggesting that the nanowire arrays have strong shape anisotropy. In this paper, we aim to present our experimental results on the effect of ac electrodeposition of CoP alloy nanowire arrays embedded in AAO templates and demonstrate the formation of an amorphous structure under different electrodeposition parameters.

anodization process. The Al foil was degreased, etched in nitric acid, and electropolished in a mixture of perchloric acid (60%) and ethanol (1:4 in volume) under 16 V below 5 C for approximately 4 min. Anodization was conducted under a constant cell potential in a 0.3 M oxalic acid electrolyte. The temperature of the electrolyte was maintained at 0 C (between 2 and +2 C) during anodization using a cooling system. The solution was stirred vigorously in order to accelerate the dispersion of the heat that evolved from the samples. The rst and second anodization steps were conducted under the same conditions mentioned above. Meanwhile, the oxide layer formed in the rst step was removed by wet chemical dissolution in a mixture of 0.2 M chromic acid and 0.4 M phosphoric acid at 60 C for an appropriate time depending on the anodizing time. The thickness of the barrier layer of oxide lm was reduced by decreasing the anodizing voltage at the end of the second step of anodization. The voltage was lowered at 2 V min1 down to 20 V and then 1 V min1 to 13 V. In the next step the anodization voltage was reduced to 12 V in a rate of 0.5 V min1 . Anodization was then continued for 8 min at this nal voltage. CoP nanowires were then ac electrodeposited into the AAO template with stainless steel as a counter-electrode at room temperature. Before electrodeposition, the AAO template was sonicated for 10 min in the electrolyte with an ultrasonic probe to facilitate wetting of the nanopores. The electrolyte solution consisted of 0.1 M CoSO4 7H2 O, 0.5 M boric acid and 0, 5, 15 and 25 g/litre NaH2 PO2 at a pH value of about 4. The root mean square (RMS) voltage used in the ac electrodeposition was 12 and 15 V at a frequency of 400 Hz with a sinusoidal waveform. Current transients were recorded during electrodeposition 24

Delivered by Ingenta to: Sahand University of Technology High purity Al foils (99.999%) were used as a substrate 3. RESULTS AND DISCUSSION IP : 80.191.211.21 to fabricate highly ordered AAO templates Thu, via a 27 doubleSep 2012 18:40:51
2. EXPERIMENTAL DETAILS

using a computer controlled A/D data acquisition system. The deposition time was determined depending on the lling time of the pores. Field emission scanning electron microscopy was used to conrm the morphology of the samples. Energy dispersive spectroscopy (EDX) (Oxford Instruments) was used to determine the chemical composition of nanowires. The crystal structure of the Co nanowires arrays were examined by X-ray diffraction. A Bruker D8 Advanced X-ray diffractometer was used, which utilizes a standard Cu tube source run at a voltage of 40 kV and lament current of 40 mA. Cu (K radiation of wavelength 0.1540496 nm is produced by this system. All 2 scans were made from incident beam angles of 35 to around 80 of the surface with detector increments of 0.05 degree every second. The magnetic properties of nanowires were investigated using homemade vibrating sample and magneto-optical Kerr effect magnetometers. The possible maximum applied eld was 2000 Oe.

RESEARCH ARTICLE

Electrodeposition of CoP nanowire arrays into highly ordered AAO template was controlled using the current transients. It is clear from the literature that nucleation and growth of nanowires takes place in nanoporous template through a four-stage process which is exploited by the current-time curves including (1) nucleation of nanowires at the pore bottoms, (2) growth of wires within the pores, (3) pore llings and (4) overgrowth, as reported by Whitney et al.13 Figure 1(a) illustrates current transients recorded during electrodeposition of CoP nanowires under a sinusoidal waveform with a frequency of 400 Hz from different solutions containing 0, 5, 15 and 25 g/litre sodium hypophosphate. The four-stage nucleation and growth mechanism is clearly observed for the electrodeposition of nanowires in AAO. However, the transients show slight differences in regard to the position of different stages and also the deposition current and its trend during the deposition. When the phosphorous does not incorporate in the reduction reaction, i.e., pure cobalt nanowires, the lling time is longer with a sharp increase exhibiting a uniform lling of nanopores.5 However, looking at the current transients of the electrodeposition from the solutions containing sodium hypophosphate reveals that stage (3) starts more quickly as long as the variation has a shallow slope during stages (2) and (3). These effects become clearer when the concentration of the phosphorous in the solution is higher. Another feature is that the deposition current decreases with increasing phosphorous content of the electrolyte. This shows that the nanopores are lled uniformly across the overall template area. A probable explanation for the increasing current during stages (2) and (3) is that poor
J. Spintron. Magn. Nanomater. 1, 2327, 2012

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AC Electrodeposition of Amorphous CoP Nanowires Embedded in an Alumina Template

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time (s)
Fig. 1. Current transients recorded during electrodeposition of CoP nanowires in AAO with an applied sinusoidal waveform with a frequency of 400 Hz (a) from different solutions containing 0, 5, 15 and 25 g/litre sodium hypophosphate at 15 Vrms and (b) from a solution containing 5 g/litre sodium hypophosphate at 12 and 15 Vrms .

RESEARCH ARTICLE

wetting leads to a delay in nucleation in some pores so that the number of pores in which growth takes place and therefore also the current, rise gradually.14 The increase in current during stage (2) and its duration are signicantly greater for the polycarbonate membranes than for the polyester ones, consistent with poorer wetting in the former case. According to Fokkink et al.14 poor porewetting also leads to a smearing out of the transition to bulk growth and it is noticeable that stage (3) is much longer for the polycarbonate than for the polyester membranes. The effect of deposition potential on the growth of CoP nanowires has also been studied. Figure 1(b) shows the current transients recorded during electrodeposition at 12 and 15 Vrms with a sinusoidal frequency of 400 Hz. The sole difference is the reduction of growth rate as the deposition potential decreases. This is evident from the crosssectional SEM image of the CoP nanowires grown in the AAO template. Figure 2 shows SEM images and a typical EDX spectrum of CoP nanowires electrodeposited at 12 Vrms . The SEM image reveals that the pores are incompletely lled with CoP nanowires after electrodeposition under 12 Vrms for 500 s. The crystalline structure of CoP nanowires electrodeposited at 15 Vrms with a frequency of 400 Hz was studied using XRD. X-ray diffraction patterns obtained from
J. Spintron. Magn. Nanomater. 1, 2327, 2012

Fig. 2. (a) SEM image and (b) a typical EDX spectrum of CoP nanowires ac electrodeposited at 12 Vrms and 400 Hz for 500 s in AAO.

CoP nanowires electrodeposited in AAO from solutions containing 0, 5, 15 and 25 g/litre sodium hypophosphate are shown in Figure 3. For Co nanowires, it is observed that the microstructure is HCP with (001), (200) and (110) Bragg diffraction lines. The electrodeposited nanowires tend to lose crystallinity when phosphorous is added to the composition, since the Bragg diffraction peaks of (002) and (001) disappear. However, the phosphorous content of the electrodeposition bath directly inuences the crystalline structure as the higher the P content in the bath, the lower the XRD peak intensity. This is shown in Figure 4 for the two Bragg diffraction peaks. The magnetic properties of CoP nanowires electrodeposited in AAO reveal a strong shape anisotropy along the wires long axis and also the effect of the phosphorous content. Figure 5(a) indicate that an easy axis of magnetization is achieves along the CoP nanowires. Also, Figure 5(b) shows magnetization curves for CoP nanowires arrays electrodeposited at 15 Vrms with a frequency of 400 Hz from different solutions, when the external eld is applied in the plane of template, i.e., perpendicular to the long axis of the wires. The main inuence of the P is seen in either on the magnetic moment or the coercivity, both of which decrease with increasing P 25

AC Electrodeposition of Amorphous CoP Nanowires Embedded in an Alumina Template

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Nasirpouri et al.

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Fig. 3. X-ray diffraction patterns obtained from CoP nanowires electrodeposited in AAO from solutions containing 0, 5, 15 and 25 g/litre with a fre- by Ingenta to: sodium hypophosphate at 15 Vrms with a sinusoidal waveform Delivered quency of 400 Hz. It should be noted that Al peaks are not seen in bottom Sahand University of Technology panel due to annealing of Al substrate before anodization.

IP : 80.191.211.21 Thu, 27 Sep 2012 18:40:51

content in the electrolyte. For coercivity change, it can be explained with the domain structure in amorphous alloys. Because, the domain walls are wide in amorphous alloys and the defects are narrow, there is little pinning of domain

Fig. 5. Magnetization curves of CoP nanowires arrays electrodeposited at 15 Vrms with a frequency of 400 Hz from (a) a solution containg 5 g/litre phosphorous content in two congurations; in-plane and out of plane of AAO template, and (b) different solutions with different phosphorous contents with an applied eld in plane of AAO template. Ms is the magnetization at the possible maximum applied eld.

RESEARCH ARTICLE

(a) 6000 Intensity (CPS)

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walls on defects in amorphous materials and coercivity decreases.15

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We have demonstrated the electrodeposition of amorphous CoP nanowires using an ac sinusoidal waveform with a frequency of 400 Hz under potentiostatic conditions from aqueous solution. The incorporation of phosphorus into the cobalt nanowires takes place during electrodeposition, making the microstructure amorphous. The Phosphorous content in the electrolyte inuence the nucleation, crystallographic structure and coercivity of CoP nanowires electrodeposited in the AAO template.

References and Notes

1. H. Zeng, R. Skomski, L. Menon, Y. Liu, S. Bandyopadhyay, and D. J. Sellmyer, Phys. Rev. B 65, 134426 (2000). 2. C. A. ross, Annu. Rev. Mater. Res. 15, R841 (2001). 3. F. Nasirpouri, Recent developments in electrodeposition and pitting research, edited by A. El-Nemr, Research Signpost Publications, India (2007), pp. 5193. 4. L. Pter and I. Bakonyi, Nanomagnetism and spintronics, edited by F. Nasirpouri and A. Nogaret, World Scientic Publishing Co, Singapore (2010), pp. 89120. 5. F. Nasirpouri, P. Southern, M. Ghorbani, A. Irajizad, and W. Schwarzacher, J. Magn. Magn. Mater. 308, 35 (2007).

2 theta
Fig. 4. Annilihitaion of Bragg diffraction peaks (a) Co (002) and (b) Co (001) for CoP nanowires electrodeposited in AAO from solutions containing 0, 5, 15 and 25 g/litre sodium hypophosphate at 15 Vrms with a sinusoidal waveform with a frequency of 400 Hz.

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AC Electrodeposition of Amorphous CoP Nanowires Embedded in an Alumina Template

12. D. S. Xue, J. L. Fu, and H. G. Shi, J. Magn. Magn. Mater. 308, 1 (2007). 13. T. M. Whitney, J. S. Jiang, P. C. Searson, and C. L. Chien, Science 261, 1316 (1993). 14. C. Schnenberger, B. M. I. van der Zande, L. G. J. Fokkink, M. Henny, C. Schmid, M. Krger, A. Bachtold, R. Huber, H. Birk, and U. Staufer, J. Phys. Chem. B 101, 5497 (1997). 15. R. C. OHandley, Modern Magnetic Materials, John Wiley and Sons, USA (2000).

6. M. Ghorbani, F. Nasirpouri, A. Irajizad, and A. Saedi, Mater. Des. 27, 983 (2006). 7. F. Nasirpouri, M. Abdollahzadeh, N. Parvini, and M. Almasi, Current Applied Physics 9, 91S (2009). 8. M. Hernandez-Velez, Thin Solid Films 495, 51 (2006). 9. T. Watanabe, Nano-plating, Elsevier, UK (2004). 10. H. Chiriac, A. E. Moga, M. Urse, I. Paduraru, and N. Lupu, J. Magn. Magn. Mater. 272, 1678 (2004). 11. J. Xu and Y. Xu, Mater. Lett. 60, 2069 (2006).

Received: 26 October 2011. Accepted: 26 November 2011.

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RESEARCH ARTICLE

J. Spintron. Magn. Nanomater. 1, 2327, 2012

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