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SCIENCE

Acts Metall. Sin. (Engl. Lett.) Vol. 19 No.4 pp307-312 Aug. 2006

DIRECT'

ACTA METALLURGICA SINICA (ENGLISH LETTERS)

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EFFECT OF ELFXTROLESS DEPOSITION CONDITIONS ON THE STRUCTURES AND THE MAGNETIC PERFORMANCES OF THE Co-Fe-P ALLOY
S.L. Wang* and F . Q . Zeng
Department of Applied Chemishy, College of Materials Science and Engineering, Huaqiao University, Quanzhou 362021, China Manuscript received 24 February 2006; in revised form 12 May 2006

Electroless Co-Fe-P alloys were deposited from an alkaline bath, containing boric acid as a buffer agent and sodium citrate as a complexing agent. As a result, with the increase of pH of the bath, the iron content of the deposit increased, whereas the cobalt and phosphorus contents decreased. The structure of the deposit was investigated using X-ray diji-action (XRO)and transmission electron microscope (TEM). The deposit consisted of hexahedron phase Co, cubic phase Fe-Co, and
amorphous phase (crystalline). ?Ize magnetic p e ~ o m c e of the deposit were studied using s

vibrating sample magnetometer (VSM). The more the content of Fe and the less the content of P (the content of Co being less), the better the magnetic pelfomnces of the deposit. The Co-Fe-P deposit was suitable for use as soft magnetic material. KEY WORDS electroless deposition; Co-Fe-P; structure; magnetic pelfonnance

1. Introduction
The magnetic thin films were key materials for various functional devices such as high-density data storage systems and read-write processes. The magnetic films plated by electroless were studied, especially Ni-Co-P['41 and CO-P[~'I alloy deposits. Because metal iron had good magnetic performances, Ni-Fe alloy and Co-Fe alloy were soft magnetic materials that were applied widely in the fabrication of magnetic memories for computer application. Electrodeposited Co-Fe-P alloy that had considerably soR magnetic performances was studied by some authors[*-"]. However, electroless Co-Fe-P alloy did not receive much attention. The effect of ferrous sulfate in the solution on the deposition rates was studied by electrochemical polarization measurements[121, the graded Co-Fe-P alloy deposit was successfblly and
'Corresponding author. Tel.: +86 595 22693746; fax: +86 595 22686969. E-mail address : slwang@hqu .edu .cn ( S .L . W a g )

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prepared[131.In this study, electroless deposition Co-Fe-P coating was studied. The relationships between the deposition conditions and the composition, and between the structure and the magnetic performances of the deposit were investigated.

2. Experimental
Co-Fe-P alloys were electrolessly deposited using a bath of the following composition: CoS04 7H20 0.06-0.09mol-L-', FeS04.7H,0 0.04-0.01mol-L-' (the total concentration of CoSO4-7H,O and FeS04. 7H,O is O.lOmol.L-'), NaH2P02-H20 0.20mol.L-', C&,07Na, 0.3Omol.L-', and H,BO, 0.50mol.L-'. The temperature was kept at 90C and the pH was adjusted to 7.0-8.5 by sodium hydroxide. Co-P alloys were prepared in the same bath and plating conditions as that of Co-Fe-P alloys, but the metallic salt was sulfate cobalt, whose concentration was 0. lOmol L-I. The composition of the deposit was determined by an energy-dispersive X-ray spectral analysis for elemental analysis (EDS, ISIS-300, Oxford Instrument) attached by a scanning electron microscope (SEM, LEO-1530). The thickness ofthese deposits was about 5.0- 10pm, which was more than the EDS required thickness of 3.Opm. The structure of the deposit was studied by X-ray dimaction (XRD) of a Rigaku D/max-RC with a Cu target radiation. The carbon steel was used as substrate in the above measurement. The structure of the deposit was also investigated by transmission electron microscope (TEM). The magnetic performance measures were made using a vibrating sample magnetometer (VSM). The sample was plated on a copper substrate whose surface area is about 0.25cm2.

3 ResultsandDiscussion .
3.1 Deposit cornposition
Fig. 1 shows a typical EDS spectrum of the deposit. It was found that the chemical composition was almost the same in different zones. The percentages in atom of the deposit elements were 71.14% cobalt, 25.90% iron, and 2.96% phosphorus. Fig.1 also shows that the coating only contains the Co, Fe, and P elements, demonstrating the purity of the coating. The relationship between pH of the bath and the deposit composition is illustrated in Fig.2. All three curves were dependent on the bath pH, but the iron and cobalt content of the deposit varied slightly below pH 7.5, and changed sharply above pH 7.7. The phosphorus content reduced slowly from 4.27% to
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Fig.1 The EDS spectrum of the Co-Fe-P deposit (molar ratio of CoSOneSO, 0.08/0.02, pH 8.0).

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posits reduced. The effect of molar ratio of CoSOJFeSO4 on the deposit composition at pH 8.0 is shown in Fig.4. The iron content of the deposit increased linearly from 12.21% to 37.79% and that of cobalt reduced linearly from 83.44% to 58.79% as the molar ratio decreased (meanwhile the concentration of FeS04 increased), whereas the phosphorus

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Fig.3 Effect of pH of the bath on the Co-P deposit composition.

Fig.4 Effect of molar ratio of CoSOfieSO, on the deposit composition (pH 8.0).

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belong to low phosphorus coating.

3.2 Deposit structure


The effect of molar ratio of CoSOdFeSO, at pH 8.0 and plating bath pH at molar ratio of CoSOd FeSO, 0.08/0.02 on the structure of the deposit is illustrated in Figs. 5 and 6, respectively. The peaks in all the XRD patterns at 26 = 41.7", 44.8", 47.6", 75.9" were (IOO), (002), (101), (110) of planes of hexahedron phase Co (P6J mm), respectively; whereas, the peaks at 28=44.6",65.0",and 82.5"were the XRD patterns of cubic phase Fe-Co phase(Zm3m). A broadened peak about 26 = 44" suggested that the deposit had an amorphous phase. Therefore, the deposits consisted of some amorphous phase, cubic phase Fe-Co, and hexahedron phase Co. At the same time, with the increase of concentration of CoS04 in the plating bath, the content of hexahedron phase Co increased, but that of cubic phase Fe-Co reduced, as shown in Fig.5. In Fig.6, with the increase of pH of the bath, the content of amorphous phase reduced, but that of cubic phase Fe-Co increased. Fig.7a shows the transmission electron microscope (TEM) image of the deposit. It was clear that some crystal lattice was ordinal and some was not ordinal. This indicated that the structure of the coating

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Fig.5 Effect of molar ratio of CoSOJFeSO, on the XRD patterns of the deposit @H 8.0).

Fig.6 Effect of the bath pH on the XRD patterns of the deposit (molar ratio of CoS0@eS04 0.08/0.02).

Fig.7 The TEM photo (a) and the electron diihction (b) of the Co-Fe-P deposit (molar ratio of CoSOfieSO, 0.08/0.02,pH 8.0).

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was also crystalline. The electron difiaction pattern corresponding to this deposit is shown in Fig.7b, which reveals the no continuous rings with intense spots inside. It further confirmed the above results. This result was not the same as that of electrodeposited Co-Fe-P alloy whose structure was but was the same as that of electrolessly deposited Co-P alloy[q.The structure of the electroless Co-Fe-P alloy was crystalline, which was related to the deposit containing low phosphorus.

3.3 Deposit magnetic per$omnce


A typical hysteresis curve of the Co-Fe-P deposit is shown in Fig.8. The deposit had high saturation magnetization (Ms) and low coercive force (HJ, which was suitable for use as soft magnetic material. The effects of molar ratio of CoSOfleSO, at pH 8.0 and plating bath pH at molar ratio of CoSOdFeSO, 0.08/0.02 on the saturation magnetization of the deposit are illustrated in Fig.9. The saturation magnetization was determined from the magnetic hysteresis curves (the figures were omitted). With the increase of the bath pH ftom 7.0 to 8.5, the saturation magnetization increased from 880 to 1180kA-m-'.Similarly, with the increase of concentration of FeS04 in the plating bath, the saturation magnetization increased from 1040 to 1261kA.m-'. On basis of magnetic theory, the saturation magnetization mainly depended on the composition of the deposit. Fe and Co atoms in 3d atomic orbital had 4 and 3 lone electrons, respectively, and so Fe atomic magnetic moment is more than that of Co. -40 -30 -20 -10 0 10 20 30 40 Thus, the saturationmagnetization of iron and cobalt Magnetic field strength H, Wm.' were 1707 and 1400kA-m-', respectively. But P Fig.8 The hysteresis curve of the Co-Fe-P deposit atom had no magnetic moment. From the above (molar ratio of CoSOJFeS04 = 0.08/0.02, studies of the deposit composition, with the increase pH 8.1). of the bath pH, the iron content of the deposit increased, whereas the cobalt and the phosphorous Molar ratio of CoSO, IFeSO, 0 0910 01 0 0810 02 0 07510 025 0 0710 03 0 06/004 content reduced. At the bath pH 8.0, with the in1300 I , crease of the concentration of FeS04, the iron content of the deposit increased, whereas the cobalt content reduced. Hence, the more the content of Fe and the less the content of P,(the content of Co being less) in the deposit, the better the magnetic performances of the deposit. The coercive force of all the deposits mainly I ranged eom 1.83 to 4.62kA.m-', the change observed was not regular. The reason was that the coercive force was sensitive to the structure of the alFig.9 Effects of the bath pH at molar ratio of loy, which depended on the structure, the disfigureCoSOfleSO, 0.08/0.02 and molar ratio of ment, the stress, the thickness of the film, and so CoSOJFeS04 at pH 8.0 on the saturation magnetization of the deposit. on.

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4. Conclusions
Electroless Co-Fe-P alloys were deposited fiom an alkaline bath, containing boric acid as a buffer agent and sodium citrate as a complexing agent. The following conclusions were drawn: with the increase of the bath pH, the iron content of the deposit increased, but the cobalt and phosphorus content reduced. With the increase of concentration of FeS04, the iron content of the deposit increased but that of cobalt reduced. The deposits plated from different conditions consisted of hexahedron phase Co, cubic phase Fe-Co, and amorphous phase (crystalline). The magnetic performances of the deposit depended on the plating conditions. The more the content of Fe and the less the content of P was in the deposit (the content of Co being less), the better the magnetic performances of the deposit. The Co-Fe-P deposit was suitable for use as soft magnetic material.

Acknowledgements-This work was supported by the Fujian Provincial Natural Science Foundation of China (No. E0210020). The authors would also like to thank Prof: L in Nanjing University for u vibrating sample magnetometer (VSM) measurements.

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