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Solid State Ionics 179 (2008) 222 227 www.elsevier.com/locate/ssi

The use of XPS for study of the surface layers of CrCo alloy electrodeposited from Cr(III) formateurea baths
S. Survilien a,, V. Jasulaitien a , A. enien a , A. Lisowska-Oleksiak b
b

Institute of Chemistry, A.Gotauto 9, 01108 Vilnius, Lithuania Technical University of Gdansk, G.Narutowicza 11/12, 80952 Gdansk, Poland

Abstract The chemical composition of the top layers of CrCo alloy electrodeposited from Cr(III) formateurea baths with various concentrations of CoCl2 was studied by the X-ray photoelectron spectroscopy method. The quantity of each element in at.% was calculated from the single Cr2p3, Co2p3, C1s, O1s and N1s peak areas. Analysis of XPS spectra has shown that the surface of CrCo alloy is covered with the thick oxide film (about 20 nm) and the bulk of the deposit consists of two phases: carbide and metallic of both chromium (about 60 at.%) and cobalt (about 3 at.%). A low percentage (about 3 at.%) of nitrogen in the bulk of the deposit suggests the presence of chromium nitrides, which may be formed along with carbides during electrodeposition owing to reduction of chromiumcarbamide complexes and an extremely high electrocatalytic activity of chromium in the cathodic processes. 2007 Elsevier B.V. All rights reserved.
Keywords: Cr-Co alloy; Electrodeposition; Formateurea bath; XPS; Morphology

1. Introduction Conventional chromium coatings electrodeposited in Cr(VI) solutions have been used for more then 100 years. Inasmuch Cr (VI) is classified among highly hazardous and toxic substances, the Cr(VI) plating process needs to be substituted by more environmentally friendly technologies. Unfortunately, few coatings could completely replace the conventional hard chromium coatings. The trivalent chromium plating process is considered as a very promising technology to replace conventional Cr coatings. However, Cr(III) based coatings showed poor corrosion resistance as compared to the coatings deposited from the Cr(VI) electrolyte [1]. The data published in [2] testify that CrC coatings electrodeposited from a Cr(III) bath may be used as alternative to conventional Cr coatings as they exhibit better wear and corrosion resistance. According to the data published in [3] Co(II) ions added to a Cr(III) bath provide superior corrosion resistance of the coating in comparison with that of Cr coating obtained in a bath without Co(II) ions. The passive film, which is formed on the surface of Cr, affects corrosion behaviour of the coating, as well.
Corresponding author. E-mail address: sveta@ktl.mii.lt (S. Survilien). 0167-2738/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.ssi.2007.12.052

As was shown in [4], the Cr coatings deposited from the Cr (III) formateurea bath contained about 2030 at.% of carbon. The analysis of the C1s spectral line has shown that the surface layers of the deposits contained considerable amounts of both organic substances and carbide compounds of chromium. To gain information on the state of carbon in the deposit bulk, the layer-by-layer etching of the chromium surface with argon gas was used. It has been determined that the bulk layers contain preferentially carbide compounds of chromium. Preliminary studies have shown that the presence of a low quantity of Co(II) ions in the Cr(III) bath enhanced the appearance of the deposits. Therefore, it was essential to determine the composition of the deposits and to define the state of elements using X-ray photoelectron spectroscopy (XPS). The aim of this work was to study the chemical composition of CrCo alloy coatings deposited from Cr(III) formateurea baths and to determine the distribution of the elements from the surface to the bulk of the deposit. 2. Experimental details Chromiumcobalt alloys were plated on copper from electrolytes containing 0.3 M of Cr2(SO4)3 6H2O, 0.6 M of Na2SO4, 0.5 M of H3BO3, 0.2 M of Al2(SO4)3 18H2O, 0.5 M of NaF, 0.4 M

. S. Surviliene et al. / Solid State Ionics 179 (2008) 222227 Table 1 Cobalt content (at.%) in the CrCo alloy deposited on the Cu substrate versus concentration of CoCl2 in Cr(III) bath, the current density (ic). and the coating thickness () Concentration of CoCl2 in Cr(III) bath g l 1 0.1 0.5 1.0 2.0 2.0 3.0 5.0 5.0 The temperature 50 C. ic A dm 2 30 30 30 20 30 20 30 20 30 m 20 30 30 0.4 30 3 15 10 5 Percentage of Co in CrCo alloy at.% 1.1 1.9 5.5 8.5 8.7 63.0 75.0 82.0 78.0

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the specimen was carried immediately to the analyzer chamber to avoid the rest gas adsorption. The quantitative elemental analysis was done by determining peak areas and taking into account empirical sensitivity factors for each element [5]. A standard program was used for data processing (XPS spectra were treated by a Shirley-type background subtraction and fitted with mixed GaussianLorentzian functions). The surface morphology of CrCo electrodeposits was examined under a scanning electronic microscope (SEM). In order to choose a typical picture for each coating, three to four locations (in the central zone) were taken. 3. Results and discussion Table 1 shows that the percentage of Co in the CrCo alloy is dramatically increased when the concentration of CoCl2 in the Cr(III) bath is 2 g l 1 and may reach 63 at.%. Such an alloy is known as CoCr alloy. It should be noted that the percentage of Co in the alloy increases with a decrease in the current density. The SEM observation data presented in Fig. 1 show a smaller size of the nodules in the middle compared to those in the peripheral region of the plated sample. Owing to the nodular growth of the deposit, the nodules extend faster in the areas of a higher current density (closer to the edges of the sample) than in the region of a lower current density (in the middle of the sample), which may essentially increase the real surface area compared to the geometrical one and, thus, the current density (at a constant current applied) will decrease during electrodeposition. Thus, the increase in the real surface area, as well as the occurrence of stable and inert oligomeric species [4], may be the reason for a decrease in the deposition rate (Table 2) during electrolysis. Fig. 2 shows that the morphology of the deposit is changed remarkably when concentration of CoCl2 in the Cr(III) bath increases up to 3 g l 1 and the percentage of Co in the alloy obtained is about 75 at.%. XPS analysis was performed to examine the elemental composition of the top layers of CrCo alloys and to determine the valence states of elements, which indicated the presence of Cr2p3, Co2p3, O1s, N1s and C1s peaks. The S2p peak at 2 169.1 eV, which shows the presence of SO4 ions, was detected only on the surface of the coating. The chemical states were identified by comparison of the photoelectron binding energies

of HCOONa and 0.75 M of (NH2)2CO as complexing agents, and additionally a low quantity (0.15 g l 1) of CoCl2. All solutions were prepared using distilled water and analytical grade chemicals. The pH of these solutions was adjusted to 2.0 0.1 by addition of H2SO4 or KOH. The copper electrode was first polished with metallographic emery paper of fine grinding and then with 5, 1 0.5 and 0.3 m aluminum slurries. The electrode was further washed with distilled water, degreased with acetone, washed with distilled water again and used as a cathode. Elemental analysis of coatings and the valence state of chromium, cobalt and other elements was studied using XPS. Spectra were recorded with a Vacuum Generator (VG) ESCALAB MK II spectrometer. The non-monochromatic Al K X-ray radiation (hv = 1486.6 eV) was used for excitation. The Al twin anode was powered at 14 kV and 20 mA. The photoelectron take-off angle was 45 with respect to the sample surface normal and spectra of Cr2p, Co2p, O1s, C1s and N1s were taken at the constant analyzer energy mode (20 eV pass energy). The base pressure was kept at below 5 10 8 Torr in the working chamber. The spectrometer was calibrated relative to Ag3d5/2 at 368.0 0.1 eV and Au4f7/2 at 83.8 0.1 eV. XPS depth profiling was performed in the preparation chamber where the argon gas pressure was maintained at 6 10 5 Torr with 50 l/s pumping speed at the gauge. The ion gun (with a cold cathode source and focus lens) was operated at 2 and 5 kV (20 A and 100 A, respectively). Every time after sputtering

Fig. 1. SEM observations of CrCo alloy surface (ic = 30 A dm 2) in the middle of sample (a) and in the peripheral region (b) of sample.

224 Table 2 The electrodeposition rate of Cr and CrCo alloy

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Concentration of CoCl2 in Time of electrolysis The rate of electrodeposition Cr(III) bath m min 1 g l 1 0 0 0 1.0 1.0 1.0 min 5 10 20 5 10 20 at 20 A dm 2 at 30 A dm 2 0.94 0.86 0.82 0.72 0.56 0.53 1.80 1.56 1.38 1.60 1.60 1.50

(BE) with those obtained from the literature [6,7]. A full width at half maximum (FWHM) of Cr2p3 in Fig. 3 suggests the presence of more than one component. The change in Cr2p3 peak positions with argon ion sputtering is conditioned by the change in the percentage of Cr0 metallic and Cr3+ in the depth of the coating [8,9]. Analysis of the data obtained shows that the Cr2p3 spectra recorded for the top layers of coating are deconvoluted into three components, whereas the one recorded for a deeper layer is deconvoluted only in two components. According to the literature data, one of the peaks (at 576.4 eV) which corresponds to Cr3+, may be attributed to the cobalt dichromiumtetraoxide (CoCr2O4) [10] and the other one (at BE = 575.0576.4 eV) to both the Cr(III) oxide and organometallic compounds [11]. The peak at BE = 574574.2 eV is a characteristic of metallic Cr0 [12], the intensity of which increases with the depth of the deposit. The peak at 577.2 eV, which is revealed in the Cr2p3 spectrum recorded for the outer layer of the coating, may be attributed to the presence of Cr(III)

Fig. 3. XPS spectra Cr2p recorded after argon sputtering for CrCo deposited from Cr(III) bath containing 1 g l 1 CoCl2 at ic = 30 A dm2.

hydroxide. It should be pointed out that the similar results were obtained for the coatings deposited at 20 A dm 2. The deconvuluted spectra of Co2p3 recorded prior to sputtering and after different sputtering times show the presence of two components in each of these levels (Fig. 4), except for the spectrum recorded for the initial surface of the coating obtained at ic = 30 A dm 2 (Fig. 4(c)). It is not easy to characterize the individual components, because BE are close for Co3O4 (around 779.6780.7 eV), CoO (780.0781.2 eV) and CoCr2O4 (780.2 eV) [13]. The peak at 778.3 0.2 eV is a characteristic of cobalt metal [14] and the peak at BE = 781.0 782.1 eV may be attributed to Co(II) hydroxide [15]. The presence of Co(OH)2 is detected through a peak at around 781.9 eV. The XPS analysis of Co2p3 spectra suggests that the

Fig. 2. Photographs of CrCo alloys (30 m) deposited from Cr(III) baths containing CoCl2 in g l 1: 0.5 (a), 1.0 (b), 2.0 (c) and 3.0 (d). Temperature 50 C and ic = 30 A dm 2.

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Fig. 4. XPS spectra Co2p3 recorded before (a, c) and after argon sputtering during 8 min at 100 A (b, d). The CrCo alloy was deposited at 20 A dm2 (a, b) and 30 A dm 2 (c, d) from Cr(III) bath containing 1.0 g l 1 CoCl2.

deposits obtained at 20 A dm 2 consist of the metal and oxide phases and the ones deposited at 30 A dm 2 additionally contain the hydroxide phase (Fig. 4(c)). This may be related to the alkalinity of the near-cathode layer owing to the increasing hydrogen evolution; therefore, Co(OH)2 is dominated in the outermost layer of the coating. The percentage of cobalt was found to be higher in the CrCo alloy deposited at 20 A dm 2 than that in the alloy deposited at 30 A dm 2. Fig. 5 shows that the O1s spectrum recorded for the initial surface of coating is deconvoluted into three components at 534.1, 532.2 and 530.2 eV with the relative intensities 1.0:8.7:2.6, respectively. The peak at 534.1 eV may be attributed to the presence of C=O and O=CO [16] and represents the contribution of organic ligands on the surface, the maximum intensity peak at 532.2 eV is assigned to the presence

of an organic compound containing amide-groups and the peak at 530.2 eV is attributed to CoO and Cr2O3. The spectra recorded after argon sputtering are deconvoluted only in two components: the maximum intensity peak at BE = 529.8 530.2 eV and the peak at BE = 531.6532.6. The O1s peak positions in the spectra recorded before and after argon sputtering show that the organic compounds dominate on the surface, whereas Cr2O3 and CoO are the dominant oxygencontaining components in the inner layers of coating. XPS data testify that the microcracks and pores are filled with oxides and organic compounds even at a depth of 400 nm. The C1s spectrum recorded on the surface of coating (Fig. 6 (a)) is deconvoluted into three components at 282.9, 285.3 and 288.9 eV with the relative intensities 1.0:5.6:2.5, respectively. The position of the peak in the C1s spectrum is associated with distinct carbide bound. The main peak at 285.3 eV may be attributed to an oxygen-containing hydrocarbon fragment [17], the peak at 288.9 eV is assigned to the presence of the organic compounds containing amide- and carboxylic-groups and a low energy component with Eb = 282.9 0.1 eV is attributed to chromium carbide (Cr3C2) [18]. The formation of Cr3C2 during chromium electrodeposition is possible due to an extremely high electrocatalytic activity of this metal in the cathodic processes [19]. The peak at 288.2 eV in Fig. 6(b) indicates the presence of an organic ligand in the top layer of the coating. After some period of argon sputtering, the deconvoluted spectra of C1s show only two components with almost unchanged relative areas (Fig. 6(df)): the main peak at 282.8 eV which is attributed to the carbide compounds, and the other one at Eb = 284.6285.1 eV. In the latter case the bond energy may be associated with the presence of both hydrocarbon fragments and coordination bonds between carbon chains and chromium atoms [17]. The deconvoluted N1s spectra show three peaks with relative areas (Fig. 7). The spectrum recorded before argon sputtering shows the main peak at 400.6 eV, which is attributed to the amide species, however, after argon sputtering the main peak

Fig. 5. XPS spectra O1s recorded before (a) and after argon sputtering at 20 A during 2 min. (b) and 5 min. (c) and at 100 A during 3 min. (d), 8 min. (e) and 20 min. (f). The CrCo alloy was deposited at 30 A dm2 from Cr(III) bath containing 1.0 g l 1 CoCl2.

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Fig. 6. XPS spectra C1s recorded before (a) and after argon sputtering at 20 A (b, c) and 100 A (df). The CrCo alloy was deposited at 30 A dm 2 from Cr(III) bath containing 1.0 g l 1 CoCl2.

positions are shifted to Eb = 396.5397.5 eV. High-energy components with Eb = 403.2402.6 eV recorded on the surface and in the near to surface layer (Fig. 7(a, b)) suggest the presence of organo-metallic compounds containing one or more amide-groups. According to the data published in [20], namely chromiumcarbamide complexes [Cr(carbamide) n(H2O)6 n]3+ are responsible for Cr electrodeposition from the Cr(III) formateurea bath. The peak positions at Eb = 396.6 02 eV and Eb = 397.5 02 eV are assigned with the presence of CrN and Cr2N, respectively. Taking into account that the reduction of Cr(III) to the metal results in the deep reduction of the organic ligand from the inner coordination sphere of the chromium complex [19], it may be assumed that the formation of nitrides

occurs simultaneously with carbides during reduction of chromium from the chromiumcarbamide complexes [20]. Table 3 shows the distribution of elements in at.% from surface to bulk of the coating. It is seen, that the atomic ratio of the main components Cr:Co varied as follows: 31, 38, 17, 16, 20, and 22. This may be related to a strong heterogeneity of asdeposited alloy, because under the soft sputtering conditions phase segregation is unlikely. It is suggested that the bulk of Cr Co alloy consists of two phases: carbide and metallic, both of which contain chromium (about 60 at.%) and cobalt (about 3 at.%). The percentage distribution of oxygen from surface to depth of the coating suggests that the surface of CrCo alloy is covered with a thick (about 20 nm) passive film containing

Fig.7. XPS spectra N1s recorded before (a) and after argon sputtering at 20 A (b, c) and 100 A (df). The CrCo alloy was deposited at 30 A dm 2 from Cr(III) bath containing 1.0 g l 1 CoCl2.

. S. Surviliene et al. / Solid State Ionics 179 (2008) 222227 Table 3 Percentages of Cr2p3, Co2p3, O1s, C1s and N1s (in at.%) detected after various argon sputtering times in top layers of CrCo alloy deposited on Cu substrate from Cr(III) bath containing 1 g l 1 CoCl2 at ic = 30 A dm 2 and T = 50 C Argon sputtering time min 0 2(20 A) (~ 8 nm) 5(20 A) (~ 20 nm) 3(100 A) (~60 nm) 8(100 A) (~160 nm) 20(100 A) (~400 nm) Cr2p3 at.% 27.76 34.86 40.38 58.60 62.32 64.52 Co2p3 at.% 0.89 0.93 2.33 3.79 3.14 2.90 O1s at.% 44.4 52.5 39.8 11.74 8.52 8.48 C1s at.% 23.67 5.04 8.64 21.16 22.38 20.70 N1s at.% 2.10 6.66 8.86 4.71 3.63 3.38

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References
[1] S. Surviliene, A. Lisowska-Oleksiak, A. Selskis, A. eunien, IMF 84 (2006) 241. [2] Zh. Zeng, L. Wang, A. Liang, J. Zhang, Electrochim. Acta 52 (2006) 1366. [3] Bento Da Fonte, Jr., Mt. Clemens Mich, US. Patent 4,359,345 (1982). [4] S. Surviliene, V. Jasulaitiene, O. Nivinskiene, A. eunien. J. Appl. Surf. Sci 253 (2007) 6738. [5] D. Briggs, M.P. Seach, Analiz Poverkhnosti Metodami Ozhe i Rentgenovskoj Fotoelektronnoj Spectroskopii, Mir, Moskva, 1987. [6] C.D. Wagner, W.M. Riggs, L.E. Davis, J.F. Moulder, G.E. Muilenberg, Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer, Minneapolis, MN, 1978 p.190. [7] C.D. Wagner, A.V. Naumkin, A. Kraut-Vass, J.W. Allison, C.J. Powell, J.R. Rumble Jr., NIST Standard Reference Database 20, Version 3.4 (Web Version). [8] V. Maurice, W.P. Yang, P. Marcus, J. Electrochem. Soc 141 (1994) 3016. [9] T.P. Moffat, R.M. Latanision, J. Electrochem. Soc 139 (1992) 1869. [10] G.C. Allen, S.J. Harris, J.A. Jutson, J.M. Dyke, Appl. Surf. Sci. 37 (1989) 111. [11] H. Biner, D. Sellman, Z. Naturforsch. B 33 (1978) 173. [12] E. Desimoni, C. Malitesta, P.G. Zambonin, J.C. Riviere. Surf. Interface Anal 13 (1988) 173. [13] M. Oku, K. Hirokawa, J. Electron Spectrosc. Relat. Phenom 8 (1976) 475. [14] S.L.T. Andersson, R.F. Howe, J. Phys. Chem. 93 (1989) 4913. [15] B.J. Tan, K.J. Klabunde, P.M.A. Sherwood, J. Am. Chem. Soc 113 (1991) 855. [16] J. Petitjean, S. Aeiyach, J.C. Lacroix, P.C. Lacaze, J. Electroanal. Chem 478 (1999) 94. [17] L.N. Vykhodtseva, E.N. Lubnin, Yu.M. Polukarov, V.A. Safonov, Russian J. Electrochem. 41 (2005) 919. [18] L. Ramqvist, K. Hamrin, G. Johansson, A. Fahlman, J. Phys. Chem. Solids 30 (1969) 1835. [19] V.A. Safonov, L.N. Vykhodtseva, Y.M. Polukarov, O.V. Safonova, G. Smolentsev, M. Sikora, S.G. Eeckhout, P. Glatzel, J. Phys. Chem. B 110 (2006) 23192. [20] S. Surviliene, O. Nivinskiene, A. Cesuniene, A. Selskis, J. Appl. Electrochem. 36 (2006) 649. [21] E.N. Lubnin, A.A. Edigaryan, Yu.M. Polukarov, Zas. Met. 36 (2000) 339.

adsorbed organic substances [4,21] and the products of interaction of metals with atmosphere (air oxide film), in which the total percentage of oxygen is 40 to 50 at.%. The presence of defects (microcracks, pinholes) filled with an oxide film and adsorbed organic substances may explain the fact that some amount of oxides and organic compounds containing about 8 at.% of oxygen was detected at a depth of 400 nm. 4. Conclusions The chemical composition of the top layers of CrCo alloys electrodeposited from Cr(III) formateurea baths with various concentrations of CoCl2 was studied by the X-ray photoelectron spectroscopy method. The XPS data show that the surface of CrCo alloy is covered with a thick oxide film (about 20 nm) and the bulk of the deposit consists of two phases: carbide and metallic of both chromium (about 60 at.%) and cobalt (about 3 at.%). A low percentage (about 3 at.%) of nitrogen in the bulk of the deposit suggests the presence of chromium nitrides, which may be formed along with carbides during electrodeposition owing to reduction of chromiumcarbamide complexes and an extremely high electrocatalytic activity of chromium in the cathodic processes.