Applied Surface Science 253 (2007) 74617466 www.elsevier.

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Effect of organic additives on characterization of electrodeposited Co-W thin lms

Guoying Wei a,*, Hongliang Ge a, Xiao Zhu a, Qiong Wu a, Junying Yu a, Baoyan Wang b
a

Zhejiang Key Lab of magnetism, College of Material Science and Technology, China Jiliang University, Hangzhou 310018, China b Hengdian Group DMEGC Magnetic Limited Company, Dongyang 310000, China Received 8 January 2007; received in revised form 3 March 2007; accepted 19 March 2007 Available online 30 March 2007

Abstract Co-W thin lms were electrodeposited from aqueous bath with different organic additives. Electrochemical analysis showed that the transient state was limited and polarization behaviors were more evident during Co-W electrodeposition in the presence of organic additives. SEM measurement indicated that the surface morphology was affected by the nature of the organic additives to a large extent. Homogeneous Co-W thin lms were obtained from the solutions containing ethyl methacrylate. Moreover, it was obvious that the presence of organic additives, in the electroplating bath, modied the structure and magnetic properties of the Co-W thin lms according to the XRD and VSM measurements. # 2007 Elsevier B.V. All rights reserved.
PACS : 81.15. Pq; 82.45. Mp; 75.70 Keywords: Electrodeposition; Co-W thin lms; Organic additives

1. Introduction Electrodeposition technique is of great interest for industrial usage. It is a straight-forward process for the production of functional and protective thin lms with low cost and easy control [14]. Practically, all commercial electroplating baths contain one or more additive agents, which help to improve the morphology and enhance physical properties of metal electrodeposits [57]. Saccharin (SAC), thiourea and other compounds are commonly used as leveling and brightening agents in electroplating industries. Electrodeposited Co-W thin lms have been used widely in modern electronic industries due to their versatile magnetic properties. Hamid recently found that the organic additives DAH and DAO had an enormous effect on the surface properties and thermodynamic properties of the Co-W alloys [8]. In order to obtain good or new characterization of electrodeposited Co-W thin lms, it is essential to discuss the effect of different organic additives on physical properties. The present study was to investigate the characterization of electrodeposited Co-W thin lms from

plating baths with different organic additives. Organic additives with two different structures, methacrylate group and sulfonamide group (Fig. 1), were added to the plating solutions. In the presence of organic additives, Co-W thin lms were electrodeposited under certain conditions. We analyzed the corresponding electrochemical dynamic behaviors, alloy structure and morphology of thin lms, respectively. Furthermore, the magnetic properties of Co-W thin lms electrodeposited from baths with different organic additives were discussed in detail. 2. Experimental 2.1. Electrolyte compositions The cobalt-tungsten electrolyte was prepared from analytical grade cobalt sulfate (CoSO47H2O, 0.1 mol/L), sodium tungstate (Na2WO42H2O, 0.05 mol/L), ammonium citrate dibasic ((NH4)2C6H6O7, 0.3 mol/L), aminoacetic acid (NH2CH2COOH, 0.2 mol/L) and sodium sulfate (Na2SO4, 0.3 mol/L). NaOH was used to adjust the electrolyte pH. The structure of saccharin (SAC), o-toluene sulfonamide (oTOL) and methacrylate reagent used as organic additives are shown in Fig. 1. Additives have been added to the bath with a

* Corresponding author. Tel.: +86 571 86914414; fax: +86 571 28911371. E-mail address: guoyingwei@sina.com (G. Wei). 0169-4332/$ see front matter # 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2007.03.045

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properties of thin lms were observed by SEM and VSM (Lakeshore7407), respectively. 3. Results and discussion 3.1. Inuence of the additives on the cathodic process
Fig. 1. Chemical structure of organic additives.

concentration of 0.002 mol/L (above their critical micelle concentration values). All the solutions were prepared using ultra-pure Millipore water. 2.2. Preparation and characterization of electrodeposited cobalt-tungsten thin lms Co-W electrodeposition was performed in a three-electrode cell. A copper plate was used as the working electrode with the surface area of 0.5 cm2; the surface was polished to a mirror nish with different alumina grades down to 0.05 mm and cleaned ultrasonically before every experiment. The platinum plate anode was about 10 times larger. All potentials are reported with respect to the Hg/HgO referring electrode. Electrolyte temperature was 50 8C, kept constant by a thermostat during electrodeposition. Current density was 20 mA cm2. The electrolyte pH was adjusted to 8.0 with either sodium hydroxide or sulphamic acid. All electrochemical measurements were carried out with a potentiostatgalvanostat connected to a PC to allow experimental control and data acquisition. The potentiostatic transients were recorded at time intervals of 0.1 s. The potentiodynamic polarization curves were performed under quiescent conditions at 10 mV/s, scanning initially from open circuit potential to 1.2 V. The structure of electrodeposited Co-W was characterized by X-ray diffraction (XRD), using an X-ray diffractometer (Philips X0 Pert, Cu Ka = 1.5405 A). Film thickness was measured by a surface proler and was kept to 0.4 mm by adjusting the deposition time; morphology and magnetic

The effects of organic additives on the electrode kinetics of the Co-W codeposition were investigated using transient techniques. Chronoamperometry curves were used in order to study the current density variation, according to the potential applied at the working electrode (from 1.055 to 1.035 V versus electrode potential of HgO/Hg). Fig. 2(a and b) shows the current density variation during Co-W electrodeposition process with or without organic additives. We can observe that both jt transients showed a normal dependence on the overpotential, and the current density increased with overpotential. The particular shapes of the jt transients (Fig. 2(b)) clearly show that a nucleation and growth process was involved for the Co-W electrodeposition in the absence of organic additives. However, the transient state was limited during Co-W electrodeposition in the presence of organic additives and the current density rapidly reached a constant value (Fig. 2(a)). The results demonstrated that the nucleation time was shorter for the Co-W electrodeposition in the presence of organic additives. To understand the effect of additives on the mechanism of Co-W codeposition, potentiodynamic polarization curves were traced in plating baths with the absence and presence of different additives (Fig. 3). Curve 1 illustrates the cathodic polarization curves for the deposition of Co-W from the solutions without organic additives. Curves 26 represent the cathodic polarization curves of Co-W electrodeposition from electrolytes with various additives. For the potential region between 0.80 and 1.20 V, the shape of the curves (curves 16) were similar but a shift to more negative potential and a decrease on the current density were observed, depending on the presence and nature of the organic additives. Comparing the cathodic polarization curve, polar-

Fig. 2. Chronoamperometry curves obtained at the copper electrode in CoSO47H2O, 0.1 mol/L; Na2WO42H2O, 0.05 mol/L; (NH4)2C6H6O7, 0.3 mol/L; NH2CH2COOH, 0.2 mol/L and Na2SO4, 0.3 mol/L: (a) in the presence of ethyl methacrylate; (b) in the absence of additives. T = 60 8C; pH 8.0.

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ization behavior was more evident in the presence of organic additives (curves 26). The comparison between the polarization curves shows that the negative shift on the potential, increased in the following order: oTOL, SAC, dibutyl methacrylate, coumarin and R-methacrylate. This result is usually interpreted by a partial coverage of the electrode surface by the additive which blocks the active sites, decreasing the nucleation rate and affecting the nucleation mechanism [9]. In addition, adsorption of the additives on the growing Co-W deposit can also occur, blocking the electrocrystallization process. This inhibition depended on the nature of the organic molecules (such as the conjugate effect) and the specic interactions between the additives and the alloy deposit. 3.2. Inuence of the additives on the surface morphology of electrodeposited thin lms It is clear that the presence of organic additives modied the electrodeposition process from the electrochemical analysis. In order to determine whether these changes were reected in the deposit morphology and composition, an SEM/EDS study was performed. The results are shown in Fig. 4. It can be noted that

Fig. 3. Cathodic polarization curves of Co-W electrodeposition from electrolytes with different additives. Electrolyte composition: CoSO47H2O, 0.1 mol/ L; Na2WO42H2O, 0.05 mol/L; (NH4)2C6H6O7, 0.3 mol/L; NH2CH2COOH, 0.2 mol/L; Na2SO4, 0.3 mol/L and 0.002 mol/L additives: 1, no organic additives; 2, 0.002 mol/L oTOL; 3, 0.002 mol/LSAC; 4, 0.002 mol/L dibutyl methacrylate; 5, 0.002 mol/L coumarin; 6, 0.002 mol/L ethyl/methyl methacrylate. T = 60 8C; pH 8.0.

Fig. 4. Scanning electron micrographs of the surface of the electrodeposited Co-W thin lms obtained in the presence of (a) ethyl methacrylate (Co: 89.11 at%; W: 10.89 at%); (b) SAC (Co: 88.36 at%; W: 10.99 at%; S: 0.65 at%); (c) oTOL (Co: 89.09 at%; W: 10.91 at%); (d) coumarin (Co: 89.42 at%; W: 10.58 at%); T = 60 8C; I = 0.01 A; pH 8.0; lm thickness: 0.4 mm.

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Fig. 5. X-ray diffraction pattern of the electrodeposited lms in the absence and in the presence of organic additives: (a) original patterns; (b) zoom-in pattern (*reexions due to the copper substrate); T = 60 8C; I = 0.01 A; pH 8.0; lm thickness: 0.4 mm.

Fig. 6. Hysteresis loops of electrodeposited Co-W thin lms from solutions with different organic additives (pH 8, T = 60 8C): (a) methyl methacrylate: Hc// = 594.58 Oe; Hc? = 853.71 Oe; Ms = 967.6 emu cm3. (b) Ethyl methacrylate: Hc// = 638.95 Oe; Hc? = 890.94 Oe; Ms = 948.1 emu cm3. (c) SAC: Hc// = 598.04 Oe; Hc? = 883.97 Oe; Ms = 874.6 emu cm3. (d) Dibutyl methacrylate: Hc// = 517.37 Oe; Hc? = 531.77 Oe; Ms = 940.8 emu cm3. (e) Coumarin: Hc// = 475.57 Oe; Hc? = 504.14 Oe; Ms = 1129.6 emu cm3. (f) oTOL: Hc// = 87.99 Oe; Hc? = 83.59 Oe; Ms = 1401.3 emu cm3. (g) No organic additives: Hc// = 565.52 Oe; Hc? = 583.27 Oe; Ms = 822.7 emu cm3. Hc// denotes the coercivity obtained when the magnetic eld was parallel to the lms plane; Hc? denotes the coercivity obtained when the magnetic eld was perpendicular to the lms plane.

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Fig. 6. (Continued ).

the surface morphology was markedly affected by the nature of the organic additives. Using ethyl methacrylate as additive, CoW thin lm was usually homogeneous and no obvious aggregate could be distinguished among used magnication (Fig. 4a). Moreover, by visual observation, we can notice that the addition of methyl methacrylate produced mirror bright deposit. In the case of SAC, deposits were bright but there were quite a few cracks in the surface (Fig. 4b). EDS analysis reveals the presence of Co, W and S. The existence of sulphur could be due to the incorporation of SAC in lms. When oTOL was used in the bath, we could note an inhomogeneous morphology with crystal aggregates of size between 5 and 7 mm (Fig. 4c). The deposits, prepared from solutions with coumarin (Fig. 4d), were inhomogeneous with crystal aggregates and cracks. We could distinguish a dark and a mat deposit by visual observation. Though pronounced variation in surface morphology was observed, there were no obvious changes in composition percentage of cobalt and tungsten. 3.3. Structure and magnetic properties of electrodeposited Co-W thin lms Fig. 5 displays the diffractograms for the Co-W thin lms obtained in the absence and presence of different organic

additives. It is clear that the presence of organic additives, in the plating bath, affected the crystallographic orientation and phase component of the deposits. In the absence of organic molecules (Fig. 5(b)), the relative intensity of the lines indicates a strong (1 0 0) orientation of Co3W. For the deposits obtained from the solutions containing SAC, methyl methacrylate and ethyl methacrylate, there are three main peaks of Co3W: (1 0 0), (0 0 2) and (2 0 1). In the case of oTOL, the most intense diffraction line is Co7W6. For the deposits prepared from dibutyl methacrylate and coumarin, reexions of Co7W6, Co3W(1 0 0), Co3W(0 0 2) and Co3W(2 0 1) appeared simultaneously. The variation of crystallographic orientation and phase component may be due to the different interactions with crystal planes, which induces the different growth mechanism [10]. In order to study the effect of organic additives on the properties of electrodeposited Co-W thin lms, vibrating sample magnetometer (VSM) was used to give the magnetic hysteresis loops of samples. Fig. 6 shows the hysteresis loops of Co-W thin lms electrodeposited from additive-containing or additive-free bath. It is interesting to note that magnetic anisotropy has been strengthened in the presence of methyl methacrylate, ethyl methacrylate and SAC. The lms prepared under these conditions were of hard magnetic properties. In the

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case of dibutyl methacrylate or coumarin, saturation magnetization increased but coercivity decreased. Co-W thin lms electrodeposited from oTOL-containing bath presented good soft magnetic properties (Ms = 1401.3 emu cm3) compared with pure cobalt thin lms (1370 emu cm3) [11]. It can be concluded that the presence of organic additives can not only improve the surface morphology and compactness, but also tailor magnetic properties of the electrodeposited Co-W thin lms. The different characterization of Co-W thin lms may attribute to the fact that presence of various additives in the plating bath can lead to the different processes of alloy deposition and growth. The detailed mechanism has not yet known. 4. Conclusions Effect of organic additives on the electrochemical behaviors of Co-W electrodeposition has been investigated by means of transient state technique and linear sweep voltammetry. The results show that the nucleation time was shorter and a shift to more negative potential was observed in the presence of organic additives. The negative shift on the potential increased in the following order: oTOL, SAC, dibutyl methacrylate, coumarin and R-methacrylate. Surface morphology, microstructure and magnetic properties were studied by SEM, XRD and VSM, respectively. It is turned out that the Co-W thin lms

electrodeposited from solutions containing different additives presented different surface morphology. Homogeneous thin lms could be obtained in the presence of ethyl methacrylate. Meanwhile, we can see that the addition of organic additives could lead to variation of structure and magnetic properties of the Co-W thin lms. Acknowledgement This work is supported by the National Natural Science Foundation of China (No. 20571067 and 20601024). Reference
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