Electrochimica Acta 49 (2004) 20412049

Characterisation of CoNi(Cu)/Cu multilayers deposited from a citrate electrolyte in a ow channel cell

S.M.S.I. Dulal , E.A. Charles, S. Roy
School of Chemical Engineering and Advanced Materials, University of Newcastle, Newcastle upon Tyne NE1 7RU, UK Received 5 September 2003; received in revised form 22 December 2003; accepted 24 December 2003

Abstract CoNi(Cu)/Cu multilayers consisting of 50 and 200 bi-layers were deposited from a citrate electrolyte in a ow channel cell by a dual pulse plating technique. The dissolution of the ferromagnetic components during pulse plating was studied using an oscilloscope and cyclic voltammetry. It was found that the dissolution was suppressed due to the passivation of the ferromagnetic layers before the deposition of an atomic layer of nonmagnetic component on them. The passivation was a function of the nickel ion concentration in the electrolyte. X-ray studies showed that the deposit had a preferred crystal orientation of [1 1 1] and suggested the formation of a super-lattice. Atomic force microscopy studies showed a four-fold increase of the roughness of the ferromagnetic surface with increasing layer thickness from 6 to 10 nm, whereas the roughness of the nonmagnetic surface only changed slightly with increasing layer thickness. The multilayers exhibit giant magnetoresistance. 2004 Elsevier Ltd. All rights reserved.
Keywords: Dissolution; Electrodeposited multilayers; Flow cell; Giant magnetoresistance; Interface simulation; Pulse plating

1. Introduction Multilayer thin lms consist of alternating layers of two or more different materials or alloys, which exhibit some unique and promising magnetic [1,2] mechanical [37] and electrical [8,9] properties, which signicantly differ from those of their base metals and alloys. The electrical resistance of a multilayer consisting of very thin alternate layers of ferromagnetic and nonmagnetic metals is a function of applied magnetic eld. The phenomenon is called giant magnetoresistance (GMR) [10,11] and has application in electronic data storage [12,13]. At present, GMR multilayers are produced by sputtering for commercial use in electronic industries, although electrochemical deposition of multilayers is a relatively simple and cheap method. Multilayers produced by this method exhibit lower GMR than multilayers produced by sputtering. Therefore, many groups are trying to improve and optimise GMR property of electrodeposited multilayers.
Corresponding author. Present address: Department of Chemistry, Pusan National University, Pusan 603-735, South Korea. Tel.: +82-51-510-3234; fax: +82-51-514-2430. E-mail address: dulal smsi@yahoo.com (S.M.S.I. Dulal).

There are two different electrochemical techniques to plate multilayer thin lmsdual bath technique and single bath technique. In dual bath technique, alternate layers of two different metals are deposited from two separate electrolytes by transferring the substrate from one bath to another. The drawbacks of this technique are the possibilities of oxidation of the deposit during substrate transferring between the baths and the contamination of the electrolytes. In single bath technique, alternate layers of two metals are obtained by depositing the noble component, generally the nonmagnetic metal, at the diffusion limiting current and then plating the less noble component, normally the ferromagnetic metal, under kinetic control. The major disadvantage of this technique is that some more noble metal 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 the 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. The single bath technique has gained

0013-4686/$ see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2003.12.038

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more popularity because it uses simpler apparatus, lowers the possibility of contamination or oxidation and is more efcient for plating layers of nanometric thickness where enhanced physical properties are often observed. Another drawback of the multilayer electrodeposition process is that the less noble metal dissolves during the deposition of the more noble metal. The problem was rst reported by Despic and Jovic [14] in the Pb/Cu system. They found that during the current off period, copper underwent a displacement reaction with lead and that lead dissolution occurred. Bradley and Landolt [15] showed that 510 monolayers of plated copper suppressed the displacement reaction during electrodeposition of Ni/Cu multilayers. A later study by them, where copper and cobalt alloys were electrodeposited from a citrate electrolyte, however, showed that the dissolution of cobalt continued for much longer time periods compared with the coppernickel system [16]. Dulal et al. [17,18] reported that cobalt and copper dissolved independently from a Cu/CoCu/Cu sandwich and that cobalt dissolution could occur beneath a copper over-layer as thick as 600 nm. They also found that when nickel was added to the electrolyte, the dissolution of cobalt was prevented due to the passivation of the ferromagnetic layer. It has been found that GMR of electrodeposited multilayers is strongly dependent on deposit quality as well as on various physical and electrochemical process parameters [1923]. GMR is attributed due to the spin dependent scattering in the multilayers, but a controversy exists concerning whether the scattering occurs within the layers or predominantly at the interface. However, Parkins [24] experiments suggest that interface scattering is important in GMR. Interface characterisation of multilayers consisting of a few nanometer thick alternate layers is often very difcult although X-ray studies can yield information about roughness [25]. In the present study CoNi(Cu)/Cu multilayers were deposited from a citrate electrolyte by a dual-pulse plating method. A citrate electrolyte has not been used previously to produce CoNi(Cu)/Cu multilayers, although many other multilayers including Ni(Cu)/Cu and Co(Cu)/Cu have been successfully produced from citrate electrolyte [2628]. In most of the previous works multilayers were deposited from stagnant electrolytes. It is well known that more dense, uniform and reproducible deposits can be obtained if plated under hydrodynamic condition. In such a condition a steady state is attained rapidly and the rate of mass transfer at the electrode surface are larger than the rates of diffusion alone. Therefore, a vertical ow channel cell has been developed at Newcastle where multilayers are deposited under controlled hydrodynamic condition and mass transfer to the electrode is dominated by forced convection. The dissolution of less noble metals during pulse plating was studied using an oscilloscope and a rotating disc electrode. The microstructural characterisation was performed using X-ray diffraction. The surface topography of the plated multilayers was studied using atomic force microscopy (AFM).

2. Experimental details CoNi(Cu)/Cu multilayers were electrodeposited from a citrate electrolyte on TiAu-coated quartz discs. The electrolyte was prepared by dissolving appropriate amount of the metal sulphate salts and tri-sodium citrate (NaCit) in de-ionised water. The free-standing pH of the electrolytes was found to be varied between 4.4 and 4.6 depending on the concentration of the electrolyte. In some cases pH was adjusted to 6 by the addition of dilute NaOH solution. The ow cell and the electrodes are shown in Fig. 1. The cross-section of the cell was rectangular and the electrolyte was circulated upward through the channel by a pump. The velocity of the uid was controlled by a motor and monitored by a digital ow meter. The height of the cell was 40 cm and the distance between the channel walls as well as between the electrodes was 3 mm. The working electrode was a TiAu-coated quartz disc. A rectangular copper block was used as a counter electrode. The copper counter electrode compensated any depletion of copper ions in the electrolyte. The surface areas of the working and counter electrodes were 0.786 and 16 cm2 , respectively. The large surface area of the counter electrode allowed its use as both counter and reference electrodes and minimised any overpotential. The geometry of the ow cell was chosen to ensure forced convection mass-transfer [29] and the ow rate was maintained in a range where laminar ow occurred through the channel (Reynolds number, Re < 2000). The conical entry and exit sections prevented the formation of any eddy at the inlet and outlet of the channel. Electrical contact between the back and the gold surface of the disc was made by painting a side of the discs wall with conducting silver paint. The back of the disc was coated with silver paint. The disc was then inserted into a Teon cap, which was dilated by placing in boiling water. The cap was left for a few minutes to cool down to room temperature. The disc sat in recess in the cap. The cap was then inserted in the electrode holder. The back of the disc was connected to a copper rod via a spring. The holder was then placed in a slot of the ow cell. The counter electrode was polished with ne silicon carbide paper and washed with de-ionised water. After drying it in the air, it was set in the other slot of the cell. As shown in Fig. 1a, a computer was used to programme an appropriate waveform that determined the charge and potential necessary to plate multilayers with desired thickness and number of layers. The required charge related to deposit thickness was calculated using Faradays laws assuming uniform deposition at 100% current efciency. An oscilloscope was connected to the potentiostat to monitor the current and potential transients with time. A potentiostat interfaced with the computer via an A/D card was used to apply the potential to the electrode. Approximately 1.5 L solution was placed in the reservoir. A ow rate of 30 or 40 cm3 s1 was maintained during deposition. All potentials were measured against the copper block, which was also

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Fig. 1. Schematic diagrams and dimensions of: (a) the ow channel cell and (b) the electrodes.

used as the counter electrode. In all cases, the low pulse potential (to deposit copper layer) was 0.6 V. The high pulse potential was either 1.8 or 2 V. Depending on applied potential and electrolyte concentration the deposition current density at high pulse varied between 110 and 135 mA cm2 . The current density for copper deposition at low pulse was

fairly stable, at 1.27 mA cm2 . The deposition was carried out at room temperature (25 3 C). After the completion of the plating process, the electrode holder was dismantled and the plated multilayer was taken carefully out from the holder. The sample was then washed with a jet of de-ionised water and dried by blowing with air.

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The polarisation experiments were carried out using a rotating disc electrode. X-ray diffraction was performed to determine the crystal orientation of the deposited multilayers and to study the formation of any superstructure. Tests were conducted using a Phillips X-ray diffractometer, with a Cu K radiation (wavelength = 0.154 nm) incident beam. The surface topography was studied using a Park M5 atomic force microscope, which used a 2 m silicon cantilever. The magnetoresistance measurement was carried out at room temperature on as-deposited samples in the current-in-plane (CIP) conguration at four-points-in-line [30]. The magnetoresistance ratio (MR) was calculated using the formula, MR = (RH R0 )/R0 , where, RH was the samples resistance in the magnetic eld H and R0 was the sample resistance when H = 0.

3. Results and discussion 3.1. Dissolution during pulse plating The dissolution of less noble metals, nickel and cobalt, during the electrodeposition of CoNi(Cu)/Cu multilayers was studied using an oscilloscope. The current transients (with time) during the pulse plating of multilayers are shown in Fig. 2. Peaks u, v and w in Fig. 2a developed due to the dissolution of the less noble metal components at the beginning of the low pulses, i.e., at the start of the deposition of the more noble metal, copper. Fig. 2b shows anodic peak

0.12 0.09 0.06 0.03 0.00 -0.03 -0.06 -0.09 -0.12 22 23 24 25 26 27 Time/s 28 29 30 31 32 u v w

(a)
0.12 0.09 0.06
Current/A

0.03 0.00 -0.03 -0.06 -0.09 -0.12 24.04 24.05 24.06 24.07 24.08 24.09 24.10 24.11 24.12 24.13 24.14

(b)

Time/s

Fig. 2. Current transients during pulse plating of a 200 CoNi(Cu) (3 nm)/Cu (2 nm) multilayers from an electrolyte containing 0.025 M Cu2+ , 0.5 M Ni2+ , 0.1 M Co2+ and 0.265 M Na3 C6 H5 O7 ; high and low pulse potentials: 2 and 0.6 V, respectively; pH: 6; ow rate: 30 cm3 s1 .

(u) from Fig. 2a in a higher resolution, a sharp rise and graduate fall of current can be seen relating to the aspect of the dissolution process. It may be noted that the height of the anodic current peaks of different pulses varies slightly. Calculations show that the anodic charges due to the dissolution are nearly the same for all the pulse waveforms. For example, the calculated anodic charges in peaks u, v and w are 0.137, 0.134 and 0.132 mC, respectively. The dissolution from the plated ferromagnetic layers results in a decrease of expected thickness of the layer. The calculated average decrease in thickness of ferromagnetic layer is about 0.06 nm, which is approximately 2% of the thickness of the layer. The gure shows that he deposition at high pulses occurs at a current density of 124 mA cm2 and copper deposition occurs at a limiting current density of 1.27 mA cm2 . Therefore, the calculated copper impurity in the ferromagnetic layer is [100(1.27/124)] approximately 1%. A second observation from the anodic dissolution currents is that the dissolution was halted within 1015 ms. There are two possibilities for how the dissolution is stopped, (a) the developing copper layer (on the ferromagnetic layer) may suppress the dissolution of less noble metal [15,16] or (b) the ferromagnetic layer may become passive [14,31]. As the copper deposition can only occur at the limiting current density of 1.27 mA cm2 , the charge of copper deposited during the dissolution of ferromagnetic components is 0.015 mC. This charge is insufcient to form a monolayer of copper (which is approximately 0.2 nm thick) on the ferromagnetic layer. Thus the suppression of the dissolution of less noble metal is not due to the formation of any copper over-layer, rather due to the passivation of the magnetic layer, which consists predominantly of nickel and cobalt. To study the effect of nickel content in the ferromagnetic layers on its dissolution, the anodic currents of electrolytes containing varying nickel ion concentration were monitored. The calculated charges due to the dissolution of ferromagnetic components during pulse plating of CoNi(Cu)/Cu multilayers from three electrolytes containing 0.6, 0.7 and 0.8 M nickel are 0.137, 0.117 and 0.110 mC, respectively. This suggests that the dissolution of less noble metal decreases with the increase of nickel ion concentration in the electrolyte. This indicates that the presence of nickel insures the passivation of the ferromagnetic layer. A further investigation on the dissolution of ferromagnetic components was carried out using a rotating disc electrode. Fig. 3 shows polarisation curves of electrolytes containing copper and cobalt ions (curve a) and copper, cobalt and nickel ions (curve b). In both cases the potential was swept from 0 V to the negative direction at the rate of 10 mV s1 . Only copper was plated on its limiting current up to 1 V as cobalt and nickel does not reduce at a potential more positive than 1 V [18,32]. Thus a copper base layer was made on the disc electrode by a potential scan from 0 to 1 V. Cobalt and nickel reduction started on the previously deposited copper layer at a potential more negative than

Current/A

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0.04
Current Density/A cm
-2

0.02 0.00 -0.02 -0.04 -0.06 -0.08 -0.10 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 Potential vs. SME/V

Fig. 3. Polarisation curves of electrolytes containing 0.0125 M CuSO4 , 0.25 M CoSO4 and 0.265 M Na3 C6 H5 O7 (curve a), and 0.025 M CuSO4 , 0.1 M CoSO4 , 0.7 M NiSO4 and 0.265 M Na3 C6 H5 O7 (curve b); electrolyte pH was 6, the speed of the rotating disc electrode was 1200 rpm and the potential was swept at the rate of 10 mV s1 .

deposit and formed a layer on the ferromagnetic layer. Thus, a sandwich of copper layerferromagnetic layercopper layer was made by potential cycling in the negative direction. In the case of an electrolyte containing copper and cobalt ions, the dissolution of the Cu/Co/Cu sandwich started at 0.4 V (curve a). It was found that at this potential cobalt dissolved from beneath the copper over-layer and copper dissolution occurred at 0 V [18,32]. When the electrolyte contained nickel ion together with cobalt and copper, the dissolution of the Cu/NiCo/Cu sandwich started at 0 V (curve b). This suggests that the presence of nickel in the electrolyte as well as in the sandwich deposit insures the passivation of the ferromagnetic layer, which prevents the dissolution of cobalt at 0.4 V. At 0 V the copper over-layer of the Cu/NiCo/Cu sandwich started to dissolve. When all the copper from this layer dissolved the stripping current fell and there developed a peak on curve b. The stripping current started to increase again at potential 0.45 V, which was due to the dissolution of the ferromagnetic layer. 3.2. X-ray diffraction Crystal orientations of the deposited multilayers were studied by X-ray diffraction. Fig. 4a shows the X-ray diffraction spectra of a TiAu-coated substrate (blank) with a

1 V and the system became kinetically controlled. The deposition of cobalt and nickel together with small amount of copper continued up to the scan limit in the negative direction. On the reverse scan the reduction of cobalt and nickel stopped at a potential around 1 V but copper continued to
50
Au[111]

Ti [004]

Intensity/Dimensionless

40 30 20 10 0 30 40 50 60 2/ 70 80 90 100
Ag [220]

(a)
50 Intensity/Dimensionless 40
Cu[111] Co[111] Ni [111] Au[111]

Ti [004]

30 20
Cu[200] Co[200] Ni [200] Cu[222] Co[222] Ni [222]

10 0 30 40

Ag [220]

50

60
2/

70

80

90

100

(b)

Fig. 4. X-ray diffraction spectra of: (a) TiAu-coated quartz substrate and (b) a 50 CoNi(Cu) (6 nm)/Cu (6 nm) multilayer deposited on the substrate.

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patch of conducting silver paint on the surface. The diffraction of the blank substrate has been performed for subtraction from subsequent deposit analysis. A very strong peak at around 2 = 38 is observed. This indicates that the gold substrate has a preferred crystal orientation of [1 1 1]. Another strong peak at around 2 = 82 is observed. This may be due to gold [2 2 2] or titanium [0 0 4]. To determine what this peak indicated, diffraction of a CrAu-coated substrate was carried out (gure not shown) and again a very strong peak at 2 = 38 was observed due to gold [1 1 1], along with a very small peak at 2 = 82 . This suggests that the peak at 2 = 82 in Fig. 4a is due to titanium [0 0 4]. A small peak at around 2 = 64 was also observed. This is possibly due to silver [2 2 0]. Other small weak peaks at 2 = 44 and at 2 = 77 may be for silver [2 0 0] and [3 1 1], because the silver paint may not have any strong crystal orientation preference. Fig. 4b shows the diffractogram of a CoNi(Cu)/Cu multilayer deposited on TiAu-coated substrate. The peak at 2 = 38 is for gold [1 1 1]. The next strong peak at 2

values between 43 and 45 indicates the preferred crystal orientation of [1 1 1] of the copper, nickel and cobalt. This indicates that the multilayer components follow the crystal orientation of the substrate. A medium sized peak at 2 values between 95 and 99 conrms the second-order reection of [1 1 1] faces of these three metals. A tiny peak at around 2 = 52 suggests the formation of [2 0 0] lattices of copper, nickel and cobalt. The lattice parameters of copper, nickel and cobalt are very close, therefore, it is normally impossible to separate their individual peaks [33,34]. From a multilayer, Bragg reection occurs from two different types of interfaces, which results in the formation of satellite peaks on both sides of the Bragg peaks. Thus it is considered as a conrmation of the formation of layered structure or super-lattice. As can be seen in Fig. 4b, there are satellites on both sides of the [1 1 1] and [2 2 2] peaks. X-ray diffraction of more than 20 multilayers with varied composition and layer thickness has been carried out. All most all the spectra show the presence of the satellites to some extent.

Fig. 5. 10 m 10 m AFM images of 50 CoNi(Cu)/Cu multilayers, where the top layers are (a) 6 nm thick CoNi(Cu) alloy, (b) 6 nm thick Cu, (c) 10 nm thick CoNi(Cu) alloy and (d) 10 nm thick Cu.

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Fig. 5. (Continued ).

3.3. Surface topography and interface simulation Fig. 5 shows AFM images of four 50 CoNi(Cu)/Cu multilayers with varied layer thickness and surfaces. Surfaces a and b are of two samples where the top layers were 6 nm CoNi(Cu) alloy and 6 nm Cu, respectively. Surfaces c and d are also of the alloy and copper top layers, respectively, but in this case the thickness of the layers was 10 nm each. The roughness of the alloy layer increases with the increase of its thickness. The average roughness (Ra ) and root mean square roughness (Rq ) of 6 nm thick CoNi(Cu) alloy (surface a) are 3.6 and 5.1 nm, respectively and those of 10 nm thick CoNi(Cu) alloy (surface c) are 12.9 and 20.7 nm, respectively. On the other hand, the surface roughness of the copper layers remains almost the same when the thickness is increased from 6 to 10 nm. For example, Ra and Rq values of surface b are 8.4 and 17.3 nm, respectively and those of surface d are 8.0 and 13.1 nm, respectively.

Based on the AFM data the growth mechanism of electrodeposited multilayers can be explained and the interface between the layers can be simulated. Although it was found from elemental analysis that copper content in the multilayers with equal sub-layer thickness (where the thickness of both nonmagnetic and ferromagnetic layers are the same) varied from 47 to 54 at.% and nickel and cobalt contents varied from 22 to 25 and 24 to 28 at.%, respectively, for the sake of simplicity the simulation is based on the assumption that they have 50% copper atoms (which builds the nonmagnetic layer) and 50% nickel + cobalt atoms. It was also assumed that the ferromagnetic layers contain 50 at.% nickel and 50 at.% cobalt and there is no impurity of the nonmagnetic metal in the ferromagnetic layers. In Fig. 6, the copper layer is depicted in dark circles, and contains some peaks on the top as in the case of surface b and d in Fig. 5. It has been found that the nucleation of cobalt on copper is much more difcult than the nucleation of nickel on copper because cobalt is immiscible on copper [18,32]. Therefore,

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(a)

Cobalt Nickel Copper

(b)
Fig. 6. Schematic diagrams of interfaces of CoNi(Cu)/Cu multilayers (a) when a bi-layer consists of 24 atomic layers and (b) when a bi-layer consists of 36 atomic layers.

it is more likely that nickel ions would start to reduce on the copper surface rst and then co-discharge of both nickel and cobalt would occur. As the troughs of the peaks of the copper surface are thermodynamically favourable sites for nickel (and cobalt) to be reduced, the nucleation of nickel should initiate at the troughs and then both the ferromagnetic components will gradually ll them. A further reduction of the ferromagnetic components, especially cobalt, preferentially would occur on nickel and cobalt than on copper because of the difculty of electrocrystallisation of cobalt on copper [18,32]. Thus, the peaks of the ferromagnetic components would develop on the troughs of the copper surface, as illustrated in Fig. 6a. When the thickness of the layers increases, more ferromagnetic materials will reduced on the developing peaks which will increase the surface roughness (Fig. 6b). In the case of very thick layers, these peaks would continue to grow and eventually develop columns of the ferromagnetic components which have also been found by other researchers in the cross-sectional images of multilayers [35,36]. Another deduction can be made from the AFM images that multilayers should have two different types of interfaces which result from the reduction of copper on CoNi(Cu) (surfaces a and c in Fig. 5) and from the deposition of CoNi(Cu) on copper (surfaces b and d in Fig. 5). Fig. 6 shows such differences between the interfaces.

3.4. Giant magnetoresistance Fig. 7 shows the variation of magnetoresistance with applied magnetic eld for a CoNi(Cu)/Cu multilayers deposited from a citrate electrolyte of pH 4.5 which consisted

0.5 0.0 -0.5

MR/%

longitudinal transverse

-1.0 -1.5 -2.0 -2.5 -9 -6 -3 0 3 Magnetic Field/kOe 6 9

Fig. 7. Magnetoresistance curves of a 200 CoNi(Cu) (3 nm)/Cu (2 nm) multilayer deposited from an electrolyte containing 0.025 M Cu2+ , 0.5 M Ni2+ , 0.1 M Co2+ and 0.265 M Na3 C6 H5 O7 ; high and low pulse potentials: 2 and 0.6 V, respectively; pH: 4.5; ow rate: 30 cm3 s1 .

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of 200 bi-layers, where the thickness of the ferromagnetic and nonmagnetic layers were 2 and 3 nm, respectively. This is typical for multilayers showing GMR behaviour, which is due to the change in the relative alignment of the magnetisation vectors of the successive ferromagnetic layers. The longitudinal magnetoresistance (LMR) was obtained when the relative directions of the magnetic eld and the electric current were parallel and the transverse magnetoresistance (TMR) was obtained when the magnetic eld and electric current were perpendicular to each other. Both the LMR and TMR components are negative, which indicates a GMR behaviour arising from spin-dependent scattering connected with the presence of interfaces. 4. Conclusions The dissolution of less noble metals during pulse plating of CoNi(Cu)/Cu multilayers from a citrate electrolyte in a ow cell were investigated. It was found that the dissolution of the less noble components was prevented within 1015 ms, well before the formation of an atomic layer of copper on the previously built ferromagnetic layer and so the suppression of dissolution is due to the passivation of the ferromagnetic layer. AFM images show that roughness of the alloy surface increases with the increase of layer thickness whereas the roughness of nonmagnetic surface does not very signicantly. Based on the surface topographies of the alloy and copper, growth mechanism of the multilayers and their interface development have been proposed. Magnetoresistance measurement shows that the multilayers exhibit GMR. Acknowledgements At the time the research was conducted S.M.S.I. Dulal was at the University of Newcastle and he wishes to acknowledge a scholarship from this university and a grant from the Charles Wallace Bangladesh Trust. The authors are very grateful to Prof. S. Bull (University of Newcastle) and Dr. L. Peter (Hungarian Academy of Sciences) for their help in AFM imaging and magnetoresistance measurement, respectively. References
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