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Materials Chemistry and Physics 108 (2008) 391396

A study on the kinetics of CoNi/Cu multilayer electrodeposition in sulfate solution

A. Dolati , S.S. Mahshid
Materials Science and Engineering Department, Sharif University of Technology, P.O. Box 11365-9466,Tehran, Iran Received 11 March 2007; received in revised form 7 October 2007; accepted 21 October 2007

Abstract Electrodeposition of the CoNi/Cu multilayer lms was carried out in sulfate solution. Cyclic voltammetry and current transient techniques were utilized to characterize the multilayer system and to obtain the nucleation and growth mechanism. The cyclic voltammograms clearly showed that electrodeposition of cobaltnickel alloy layer was controlled by a kinetic process, where copper ions were reduced under diffusion-controlled mechanism. In addition, the current transients revealed that nucleation mechanism was instantaneous with a typical three-dimensional growth process. The microstructure of the CoNi/Cu lms was also changed with overpotential. In this system, the growth of multilayer lms was observed as layer-by-layer structure up to 1.3 V versus SCE. 2007 Elsevier B.V. All rights reserved.
Keywords: Alloy; Multilayers; Electrochemical techniques

1. Introduction Multilayer structures of alternating magnetic and nonmagnetic layers have been studied because of their applications as magnetosensories and magnetic memories. Having layers with the individual thickness of a few nanometers, these structures have displayed the giant magnetoresistance (GMR) effect [17]. This has been extensively studied with the observation of electrical resistance changes induced by an applied external magnetic eld in magnetic/non magnetic superlattices [813]. GMR effect has also observed in several metallic systems and extended to magnetic granular structures [1214]. Multilayer systems have been produced using the different methods such as sputtering, evaporation, molecular beam epitaxy and electrodeposition. Among these methods, the electrodeposition technique was a simple and inexpensive method for producing multilayers, since physical methods were performed in an ultra-high vacuum environment [1519]. In this method, it was possible to control the lm composition and thickness of multilayer in an atomic order by regulating the pulse amplitude and width [20]. The NiFe/Cu multilayer system showed antiferromagnetic coupling and moderate saturation elds combined with a

Corresponding author. Tel.: +98 21 66165201; fax: +98 21 66005717. E-mail address: dolati@sharif.edu (A. Dolati).

large GMR effect [21,22]. Regarding to high application potential, the material combination CoNi/Cu has also raised great interests because of its GMR characteristic [23]. By addition of the Co in the Ni/Cu multilayers or the Ni in the Co/Cu multilayers, enhancement of the relative eld sensitivity [24] and resistivity were possible due to the dissolution of the less noble layer [25]. When electrodeposition was used to synthesis of a multilayer system, it showed many advantages; the low temperature of deposition which reduced the interdiffusion between nanometric layers, the lm thickness was controlled by measuring the amount of charge delivered, composition was also controlled through the applied overpotential [26,27]. There were two general techniques for deposition of several systems due to some references: dual-bath and single-bath deposition [28,29]. The single-bath technique was ideal for producing nanostructures with a nearly unlimited number of layers. It was obvious that the concentration and deposition potential of each layer were the main factor in single-bath deposition. In magnetic/nonmagnetic multilayer systems, the ferromagnetic layer based on Ni and Co always unavoidably contained some amount of the nonmagnetic, noble metal Cu due to the applied two-pulse plating technique using a single bath for the multilayer deposition. This technique was relied on the fact that at a sufciently low deposition potential, only the nonmagnetic, noble metal (Cu) was deposited whereas at a high deposition

0254-0584/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2007.10.012

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potential, both Cu and the less noble, magnetic elements (Ni and Co) were co-deposited. By using an electrolyte in which the concentration of the Cu ions was much less (typically by a factor of 10100) than that the ions of the magnetic elements (Ni2+ , Co2+ ), during the low-potential pulse a pure Cu layer was obtained, whereas during the high-potential pulse a magnetic layer containing Cu typically in an amount of 110 at% can be obtained. At such a small amount of the Cu, the magnetic layers were still ferromagnetic at room temperature. Therefore, these electrodeposited multilayers were well suited for the occurrence of the GMR phenomenon [12,25,30,31]. In this study, the kinetics of Cu and cobaltnickel layers electrodeposition was investigated in sulfate solution by electrochemical techniques. The thickness and chemical composition of the Cu and CoNi layers were controlled by overpotential and ions ratio in electrolyte. The multilayer structure was also studied by AFM microscopy at the different overpotentials.
2. Experimental
Electrochemical measurements were carried out in a typical three-electrode cell. GOG (gold on glass) substrates were used as working electrode as well as a 2 cm 2 cm platinum plate for counter electrode. Potentials were recorded with respect to the saturated calomel electrode (SCE). Solution was prepared by dissolving of components in the triply distilled water as shown in Table 1. All experiments were taken in temperature 25 C and pH was measured by an EDT pH meter. Electrochemical experiments were controlled by an EG&G PAR potentiostat model 273A and software M271. Cyclic voltammetric curves were recorded for reduction of the Co2+ , Ni2+ and Cu2+ ions and the corresponding dissolution of respective deposits as a function of scan rate. The voltammetric scans were taken in the potential range from 0.8 to 1.5 V versus SCE, at the scan rates from 10 up to 200 mVs1 . The potentiostatic it transients were recorded to characterize system at pulse times of 2 s for the Cu and the CoNi layers. The double chronoamperometry curves were also utilized for deposition of multilayer at the different overpotentials. In this case, the potential was regularly stepped from 0 to 0.8 V versus SCE for the Cu reduction and then was stepped to 1.0 V versus SCE up to 1.5 V versus SCE (every 50 mV) for the CoNi layer deposition. Composition of layers was analyzed by atomic absorption techniques (AAS). The morphology of multilayer deposits was characterized by AFM microscopy model Veeco CP Research.

3. Results and discussion Cyclic voltammograms are used to determine the reduction potential regions for Co, Ni and Cu electrodeposition. Typical cyclic voltammograms are shown in Fig. 1a for deposition of the Cu, CoCu and CoNiCu systems, in solutions 13 and at the scan rate 20 mVs1 . In these curves, the initiation of the Cu reduction peak is more positive than that the Co and Ni species about 200 mV versus SCE. Also, Co is reduced at the potential more cathodic than 450 mV versus SCE as well as Ni deposition at potential 800 mV versus SCE. In curve 1, a
Table 1 Composition of solutions considered in the present study H3 BO3 (M) 0.4 0.4 0.4 NiSO4 (M) 0.2 CoSO4 (M) 0.15 0.15 CuSO4 (M) 0.001 0.001 0.001 Solutions 1 2 3

Fig. 1. (a) Cyclic voltammograms for deposition of the Cu (sol. 1), CoCu (sol. 2) and CoNiCu (sol. 3); (b) the effect of scan rate on the Cu reduction peaks (sol. 1); (c) the effect of scan rate on the CoNi deposition peaks (sol. 3).

single cathodic peak is observed at 400 mV versus SCE for single Cu solution, but the dual cathodic peaks are observed for deposition of Cu and Ni in curve 3, respectively. As shown in curve 2, at the potentials from 0.8 to 1.0 V versus SCE, another reduction peak is observed due to kinetic deposition of Ni cathions. Therefore, the resulted deposit in this potential range must be composed predominantly with Ni. Co reduction range is observed between Cu and Ni peaks in curve 2. For detailed study of electrochemical behavior of Cu, Co and Ni deposition, different experiments are derived at the potential

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range from 100 to 1500 mV versus SCE at the different scan rates, as shown in Fig. 1b and c. In these cases, deposition of Cu is initiated at potential 0.2 V versus SCE with a typical diffusion peak at potential 0.4 V versus SCE. The Cu reduction peaks are transferred to higher currents and more cathodic potentials with increasing of scan rate, attributed to diffusioncontrolled deposition (Fig. 1b). At more cathodic potentials as shown Fig. 1c, Co and Ni are deposited simultaneously with hydrogen reduction at the increasing section of curves (more cathodic potential than that 950 mV vs. SCE). At this condition, Co and Ni deposition is occurred as kinetic-controlled deposition with favorable reduction rate, at the different scan rates. It is worth to note that Cu is deposited under diffusion control at these potentials with lower deposition rate. It can be concluded that at potentials more cathodic than that 0.8 V versus SCE, the CoNi alloy deposits as the main kinetic system. In modulated compositional system (single bath technique), alternate layers of two metals can be obtained only by depositing the noble Cu component at the diffusion limiting current and then deposition of the less noble CoNi components under kinetic control [30,31]. Therefore, multilayer systems can be deposited by controlling the kinetic behavior. Chronoamperometry analyses have utilized to study the nucleation and growth mechanism of deposits. Typical current density transient curves are shown in Fig. 2 at the negative potential regions from 0.9 to 1.5 V versus SCE correspond to voltammetry peaks in Fig. 1. At potentials more positive than that 600 mV versus SCE, only Cu deposition peak is recorded. In Fig. 2a, each transient has two well-dened recognizable current density regions as a clear rst peak followed by a sharp fall and subsequent growth is observed at the more cathodic potentials. This behavior is changed with addition of Cu and Ni to Co solution in Fig. 2b and c, attributed to deposition of the Co and CoNi alloy on the deposited Cu layer. The it transients show also a normal dependence on overpotential. Moreover, the particular shapes of it transients clearly show that a nucleation and growth process is involved for the Co, CoCu and CoNiCu deposition. The transients are qualitatively consistent with the models for nucleation of 3D clusters and polarized growth, especially with increasing of overpotential. The critical time for nucleation also decreases at more negative potentials, indicating an increase of the nucleation and growth rate. In this case, polarization becomes mainly the rate-limiting process for the CoCu and CoNiCu deposition. To conrm of the nucleation and growth mechanism, it transient curves are plotted in Fig. 3 for the Co, CoCu and CoNiCu systems. It is worth to note that nucleation time is increased in the CoCu and CoNiCu solutions, indicating a change of nucleation system on the electrodeposited Cu layer. In these cases, the nucleation rate is also decreased and so deposits will be planner than that the Co deposits. In Fig. 3b, an increase at potential to 1.3 V versus SCE means that the number of nucleation sites increases and so nucleation time is decreased, but the nucleation and growth mechanism is same. In Fig. 4, double chronoamperometry curves are utilized for characterization of deposition mechanism of the Co/Cu and CoNi/Cu multilayers on the platinum electrode surface. In these

Fig. 2. Potentiostatic it transients of (a) Co (sol. 1), (b) CoCu (sol. 2) and (c) CoNiCu (sol. 3) deposits, potential range from 0.9 to 1.5 V vs. SCE.

experiments, the different sandwich layers of the Co/Cu and CoNi/Cu multilayers are produced at the different potentials of 0.8 V versus SCE (intermediate Cu layer) and potentials from 1 to 1.5 V versus SCE (Co or CoNi layer). The rst Cu layer is deposited on the platinum surface in xed condition (2 s deposition at the potential 0.8 V vs. SCE) as intermediate Cu layers. The resulting data are overlaid together where the electrochemical behavior of Cu layer is same during all of experiments. But, as shown in Fig. 4, the slope of the deposition curve is increased by increasing the potential of the Co or CoNi deposition; so the deposition rate of the second layer is dependent on deposition overpotential of the Co or CoNi layer. In

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Fig. 3. The adjustment of it transients of the Co (sol. 1), CoCu (sol. 2) and CoNiCu (sol. 3) deposited at (a) 1.1 and (b) 1.3 V vs. SCE.

Fig. 4. Potentiostatic it transients for deposition of (a) CoCu (sol. 2), (b) CoNi/Cu (sol. 3) double layers; pH 3, potential range from 1 to 1.5 V vs. SCE.

this case, the rate of nucleation and growth of the Co or CoNi on the Cu layer is increased with increasing of overpotential. It can be deduced from above experiments and the results of AAS experiments presented in Table 2 that at the lower potentials below 1 V versus SCE, composition of alloy deposit predominantly consists of Cu, while at potentials more cathodic than that 1.2 V versus SCE composition mainly consists of Co and Ni. Therefore, it can be concluded that by switching of potentials, composition-modulated CoNi/Cu multilayer can be produced in deposition interval from 0.8 to 1.3 V versus SCE. The major disadvantage is that some more noble metal
Table 2 The chemical composition of the CoNi/Cu alloy deposits as a function of potential Potential (V) 0.8 0.85 0.9 1 1.05 1.1 1.2 1.3 1.4 1.5 Cu (wt%) 28 26 20 13 11 9 6 3 1 1 Co (wt%) 38 37 39 41 46 48 55 83 85 86 Ni (wt%) 34 37 41 46 43 43 39 14 14 13

is co-deposited during the deposition of less noble component and it is not possible to deposit a pure ferromagnetic layer from single electrolyte. However, if the concentration of more noble metal in electrolyte is very low and it is plated at the diffusion limiting current, an alloy layer rich in less noble component is plated at high pulse. Thus, the impurity of more noble metal in the ferromagnetic layers can be kept as low as 13% using an electrolyte of less noble metal ion concentration 1020 times higher than that of the more noble metal [30,31]. The current transient curves for the several multilayers of the Co and CoNi deposits are shown in Fig. 5. When the secondary Co or CoNi layer is deposited on the enhanced Cu surface whole of the surface must be covered by the Cu layer, where nal deposition of the Co or CoNi layer will be independent of deposition time of intermediate Cu layer. In this case, by increasing of layers the maxima of current transient peak is occurred at the lower time and higher current densities, which means that the deposition of Co and Ni occurred with higher nucleation densities. In order to observe the structure of the CoNi/Cu multilayer, morphological analysis is performed by AFM microscope. The structure of CoNi/Cu multilayer is shown in Fig. 6 at potential 1.3 V versus SCE. In this case, the grains display a typical equally rounded shape with diameter about 200300 nm and the coverage of CoNi grains is clearly observed, where the

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Fig. 5. Potentiostatic it transients for deposition of CoNi/Cu (sol. 3) multilayers; pH 3, 20 bilayers.

Fig. 6. AFM images for deposition of [CoNi (10 nm)/Cu (2 nm)]20 multilayers at the potentials 0.8 V for the rst layers and 1.3 V for the second layers.

distance between grains is within 12 nm by AFM image analysis. Therefore, the grains can be grown with the same rate, creating a number of equally sized grains as a plan growth structure. The deposits are created as layer by layer in the CoNi/Cu system with instantaneous nucleation and growth process. 4. Conclusion The cyclic voltammetry results clearly show that electrodeposition of CoNi alloy was controlled by a kinetic process, while reduction of Cu2+ ions was as a diffusion-controlled process. In addition, the current transients reveal that nucleation

mechanism is instantaneous with a typical three-dimensional nucleation and growth process. In this system, the deposition of Cu and CoNi alloy layers is carried out easily by control of overpotential between mentioned deposition potentials. However, the growth of multilayer lms was observed as layer-by-layer structure by AFM images. References
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