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JOURNAL OF IRON AND STEEL RESEARCH, INTERNATIONAL. 2007, 14(4): 65-68

Influence of Bath Composition on Magnetic Properties of Electrodeposited Co-Pt-W Thin Films

GE Hong-liang ,
WE1 Guo-ying

WU Qiong,

ZHOU Qiao-ying

WANG Xin-yan

(College of Material Science and Engineering, China Jiliang University, Hangzhou 310018, Zhejiang , China)

Abstract: Effect of bath composition <[Co]/[Pt] and [WO:-], [tit-]) and p H on the magnetic properties of electrodeposited Co-Pt-W thin films has been investigated. Electrodeposited Co-Pt-W thin films exhibited strong perpendicular magnetic anisotropy when the ratio of [Co] to [Pt ] was 10; cathode current efficiency and perpendicular magnetic anisotropy showed little variations when [WOf-] was lower than 0. 1 mol/L, but perpendicular magnetic anisotropy had strengthened when [WO,-] was over 0. 1 mol/L, which could be explained by the fact that the hydrogen evolution could produce pores as magnetic domain pinnings; citrate as complexing reagent can promote the polarization of [Cozf] and [Pt]. As a result, the equilibrium electrode potentials of cobalt and platinum moved to negative direction, which Ied to the co-deposition of Co, P t , and W. It was also found out that the as-deposited CoPt-W hard magnetic thin films were very homogeneous, smooth, and had the maximum coercivity for the bath p H 8. 5 and the concentration of citrate 0. 26 mol/L. Key words: electrodeposition; Co-Pt-W thin film; magnetic property; bath composition

Conventional casting techniques are inadequate to manufacture micromagnets, whereas electrodeposition of permanent micromagnets is a simple and low cost manufacturing technique, which would allow the production of magnetic devices with controlled geometry, like proximity sensors, electric wrist watches, microactuators or micromotors, miniaturised relays and magnetic layers for high-density magnetic recording. Electrodeposition is also a suitable alternative technique for the easy control of structure growth and shape of the electrodeposited magnetic films at microscopic level, in comparison even with molecular beam epitaxy (MBE) or sputtering. Much interest has been growing towards the electrodeposition of cobalt alloy films due to extensive application in perpendicular high-density magnetic recording media and micro magnet^"-^'. Especially, Co-Pt thin films, which are interesting materials with high coercivity , strong perpendicular anisotropy and good corrosion resistance, have required special Recent research has shown that by adding a third element, W or Zn, the mag-

netic properties of the Co-Pt alloys with less P t content at high thickness can be increased[ll. Franz S has found that by increasing ammonia in the electrolyte, the W content increases from 1. 5 % to 3 % and the P t content decreases from 1 4 % to 8%. Increasing Pt p-salt concentration in the electrolyte, Pt content in the deposit increases from 2 % to about 1 5 % , while tungsten and cobalt contents decrease, respectively, from 1 2 % to 4 % and from 88% to 8 2 % ( i n atomic percent)[*. T h e above research has indicated that bath composition can have an enormous effect on the electrodeposited thin films. I n this study, the effects of Co2+ ]/[ Pt 1, [ W O f - 3 and bath composition <[ [cit-1) and pH on the magnetic properties of electrodeposited G P t - W ( P ) thin films are investigated.

1 Experimental Detail
T h e electrolyte involves the following chemicals: C o ( N H , S 0 3 ) , ( A R ) , ( N H , ) , P t C l , ( A R ) , Na,W04 2 H 2 0 ( A R ) , and ( N H , l z C B H s O 7 ( A R ) . Co-Pt-W films were electrodeposited in a three-

Foundation Item: Item Sponsored by National Natural Science Foundation of China (20571067) Biography:GE Hong-liang(l964-), Male, Doctor, Professor; E-mail: hongliang-ge@cjlu. edu. cn;

Revised Date: September 1, 2006

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electrode glass cell. T h e substrates were copper sheets, A platinum sheet was used as a n anode and the reference clectrode was a saturated calomel electrode ( SCE). Electrolyte temperature was 60 c I which was kept constant during electrodeposition. Current was supplied to the cell by means of a power supply in constant current mode. T h e current density was 12 mA cm-. T h e electrolyte pH was adjusted with either sodium hydroxide o r sulphamic acid. T h e chemical composition of thin films was measured by energy dispersive spectrometer (EDS) ( J E D 2 0 0 1 , J E O L ) analysis. Hysteresis loops were determined by vibrating sample magnetometer ( V S M ) (LakeShorc 7407) in magnetic field both perpendicular and parallel to the substrate. T h e phase structure and texture of deposited films were determined by X-ray diffractometry ( X R D ) ( X Pert MPD Philips P W 1830 ). SEM ( Cambridge Stereoscan 360) was used to examine thc morphology of the films.

Results and Discussion

In order to understand the effect of electrolyte
0.020

composition on the electrodeposited alloys, t h c different solutions with different [ Co2+]/[ P t ] were prepared. T h e Co-Pt-W thin films were electrodeposited at the temperature of 60 C. Fig. 1 shows the hysteresis loops of Co-Pt-W electrodeposited from the solutions with different [Co]/[PtN I t can be seen that there was a transition from soft magnetism to hard magnetism in Co-Pt-W thin films when t h e value of [ Co2- ]/[ Ptn ] changed from 0. 1 to 100. T h e electrodeposited Co-Pt-W thin films exhibited strong perpendicular magnetic anisotropy when the ratio of [Co*-] t o [Pt] was 10. Because tungsten cannot be deposited from any aqueous solvent unless there is a t least one alloying element from the iron group transition metals, tungstate concentration can have effect on properties of elcctrodeposited thin films. T h e effect of tungstate concentration on the magnetic properties of Co-Pt-W thin films is also investigated. Table 1 demonstrates variation of the cathode current efficiency and the coercivities with tungstate concentration. When [WOi-] was lower than 0. 1 m o l / L , the atomic percentage of W in Co-Pt-W changed little and the speed of hydrogen evolution w a s very low.

1.

n.03 1

n.010

0.02 0.01

0 -0.01

-0.010
-0.02
r

F -0.020
I) 0 3

-0.03

0.02
(1.01
0

-0.(11

-0.02
-0.0:3

( a ) [Co*-!/[Pt=O.

1;

(b) [CoZ-]/[Pth]=l;

(c) [Co ]/[Ptn]=lO:

(d) [CoL+[J/[PtN1=lOO

Fig. 1 Hysteresis loops of Co-Pt-W electrodeposited from solutions with different values of [Co+] [Pth 1, [WO:-]=O. 27 mol/L; current density 12 mA/cmz

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Influence of Bath Composition on Magnetic Properties of Electrodeposited Co-Pt-W Thin Films

67

Table 1
Tungstate concentration/ (mol * L-' )
0. 02 0. 04
0. 06

Variation of cathode current efficiency and coercivities with tungstate concentration

Coercivity Cathode current efficiency/ %

IOU

10n L

170

Hd/ / (kA * rn-"

54. 802 56. 641 60.383 59.659
60. 678

H,L / (kA rn-l)

160 150 140 130 120

68. 3 69. 5 68. 6 67. 4

55. 216 57.429

60. 758

0. 08
0. 10 0. 14
0. 18

61. 530
71.236 95.886 116. 221 131. 954 151. 697 179.431

62. 8
53.9 50. 7 48. 5 45. 9
46. 7

63.791 87.008 105. 241 122. 153 142.582

110 100 90

0. 22 0. 26 0. 27

Therefore, the cathode current efficiency and perpendicular magnetic anisotropy showed little variations; but when [WOi-] was over 0 . 1 mol/L, perpendicular magnetic anisotropy had strengthened, which was due to the fact that abundant hydrogen appeared at the cathode. Besides the reduction of metal ions, there was the following reaction in the copper substrate: $'= -0.828 V 2 H z 0 + 2 e - =Hz f 2 0 H The hydrogen could produce pores as magnetic domain pinnings, which would enhance the perpendicular magnetic anisotropy (PMA) of thin films. The addition of additive complexes to the electrolyte solutions can improve the physical properties of electrodeposited thin films. For Co2+ species, citrate is a good complexing reagentCg1, which can promote the polarization of CoZf and P t N for Co-Pt-W electrodeposition. As a result, the equilibrium electrode potentials of cobalt and platinum moved to negative direction, which led t o the co-deposition of Co, P t , and W. In addition, the concentration of citrate in solution can affect the properties of deposits. Fig. 2 demonstrated the effect of the citrate concentration on the coercivities of thin films. T h e dash line shows the coercivity variation of thin films perpendicular to the magnetic field ; the solid line shows the coercivity variation of thin films parallel t o the magnetic field. It can be seen that the coercivities of thin films reached the maximum when citrate was 0. 26 mol/L. More citrate can help in the formation of high-coordinating metal complexes, which would make the alloy electrodeposition more difficult and decrease the coercivities of thin films.

Fig. 2 Effect of citrate concentration on coercities of thin films (current density was 12 rnA/crnz )

Under different bath p H , there were different coordinating species. For example, the coordinating species was Hcit- at lower p H and cit- was the main coordinating species when the bath pH was over 7. 0. The different coordinating species can form different structures of metal complexes. Thus, different physical properties happened to electrodeposition of CoPt-W thin films due to the different bath pH. Fig. 3 shows the relationship between p H value of electrolyte and coercivities of thin films. It has also been found out that the as-deposited Co-Pt-W hard magnetic thin films was very homogenous, smooth, and had the maximum coercivity with the bath p H of 8. 5 and the concentration of citrate being 0. 26 mol/L, see Fig. 4. This is the result of the complete complexation of C o Z f , Pt" and W" with citrate and the disperse ability of solution was improved under this condition.
140 130 120 110
h

YE

100

-j 90

x Q

N
70

60
50 6.0 7.0 pH value 8.0 9.0

Fig. 3

Relationship between pH value of electrolyte and coercivities of thin films

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( 3 ) T h e as-deposited Co-Pt-W hard magnetic thin films were homogeneous and smooth, and had the maximum coercivity for the bath p H of 8. 5 and the concentration of citrate being 0. 26 mol/L.
References:
Duch M. Electrodeposited Co-Ni Alloys for MEMS [J]. J Micromech Microeng, 2002, 1 2 : 400-405. Nosang V M . Park D Y , Yo0 B Y . Development of Electroplated Magnetic Materials for MEMS [J]. Journal of Magnetism and Magnetic Materials. 2003, 265(2) :189.198. Park D Y I Yo0 B Y . Kelcher S , et al. Electrodeposition of Low-Stress High Magnetic Moment F e R i c h FeCoNi Thin Films [J]. Electrochimica Acta, 2006, 5 1 ( 1 2 ) : 2523-2530. lulica Zana. Giovanni Zangari. Co-Pt Micromagnets by Electro deposition [J]. Journal of Applied Physics, 2002, 91 (10): 7 320-7 3 22. Franz S, Cavallotti P L , Bestetti M , et al. Electrodeposition of Cobalt Platinum Alloys Micromagnets [J]. Journal of Magnetism and Magnetic Materials, 2004, 272-276: 2430-2431. Fernando M F R , Coey J M D. Structural Characterization and Magnetic Properties of Electrodeposited Copt Alloys [J]. Jour nal of Magnetism and Magnetic Materials, 2004, 272-276: E883-E884. Cavallotti P L , Lecis N,Gobbato G L. Comportamento Tribologic0 di Leghe Co-W-P Elettrodeposte [J]. Metallurgia Italiana, 2001, 9 3 ( 4 ) : 33-37.

Fig. 4 Surface morphology of electrodeposited Co-Pt-W thin films (bath pH: 8. 5 ; current density: 12 mA/cm ; citrate concentration: 0. 26 mol/L)

Conclusions

Magnetic properties of electro deposited Co-PtW thin films under diiferent electrodeposition conditions were studied. T h e results arc a s follows: ( 1 T h e electrodeposited Co-Pt-W thin films exhibited strong perpendicular magnetic anisotropy when the ratio of [Co2- 3 and [Pt 3 was 10 and [WO:-j was over 0. 1 mol:!L; ( 2 ) As a complexing agent. citrate can promote the polarization of [Co-] and [Pt ]. T h e coercivities of thin films reached the maximum when citrate was 0. 26 mol/L; the coercivities of Co-Pt-W alloy deposited from the solutions with more citrate would dccreasc;

Franz S. Bestetti M , Consonni M. Electrodeposition of Micromagnets of CoPtW(P) Alloys [J]. Microelectronic Engineering, 2002, 64(1-4): 487-494. lnnocenzo G C, Maria G. Study of the Electrochemical Deposition and Properties of Cobalt Oxide Species in Citrate Alkaline Solutions [J]. Journal of Electroanalytical Chemistry, 2002, 5 3 4 ( 1 ) : 31-38.