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Acts Metall. Sin. (Engl. Lett.) Vol. 19 No.4 pp307-312 Aug. 2006
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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 )
308 .
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
.~
Fe co
co
co
1
0
6
Energy, keV
10
Fig.1 The EDS spectrum of the Co-Fe-P deposit (molar ratio of CoSOneSO, 0.08/0.02, pH 8.0).
309 .
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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P
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30
20
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Fig.4 Effect of molar ratio of CoSOfieSO, on the deposit composition (pH 8.0).
310
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m
c .
i -
L .
.I
pH 8.5.
I
30 40
50 60 70
.L
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60
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80
90 28, deg
. pH7.5.
100 110 120
80
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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).
311 .
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.
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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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