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Electrochimica Acta 45 (2000) 3311 3321 www.elsevier.

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Electrodeposition of highly functional thin lms for magnetic recording devices of the next century
Tetsuya Osaka *
Department of Applied Chemistry, School of Science and Engineering, Kagami Memorial Laboratory for Materials Science and Technology, Waseda Uni6ersity, 3 -4 -1 Okubo, Shinjuku-ku, Tokyo 169 -8555, Japan Received 23 November 1999; received in revised form 15 January 2000

Abstract A review is presented of the recent progress in research and development of soft magnetic lms for magnetic recording heads of the future primarily on the basis of the work performed by the authors research group. Films of CoNiFe ternary alloy with high saturation magnetic ux density BS and low coercivity, HC were successfully produced by electrodeposition. A typical lm, designed as HB-CoNiFe, had the composition of Co65Ni12Fe23 (at.%) with BS =2.02.1 T and HC B2 Oe. Properties other than BS and HC were also investigated; namely, magnetostriction, uS, corrosion properties, and lm resistivity z. The key to the success in obtaining low HC with high BS was to form lm with very ne crystals. The inclusion of small amount of sulfur was found to be essential for producing such a lm with the desired magnetic properties. The lm has been applied to the construction of a new type of merged-GMR head, which is considered as a breakthrough for materializing ultra high-density magnetic recording. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Electrodeposition; Soft magnetic lm; High BS lm; High z lm; CoNiFe alloy

1. Introduction Fig. 1 shows how rapidly the areal density of hard disk drives (HDDs) has been increasing over the past 15-year period. Several critical innovations were necessary to bring about such a rapid progress in the eld of magnetic recording. One of the most signicant innovations from the viewpoints of material improvement is the electrodeposition of permalloy (Ni80Fe20), which was introduced by IBM in 1979 as the core material of a thin lm inductive head to increase the magnetic recording density [1]. After the introduction by IBM in 1991 of the magneto-resistive (MR) element as read


Pergamon Medal Award Lecture * Tel.: +81-3-52863202; fax: + 81-3-32052074. E-mail address: osakatet@mn.waseda.ac.jp (T. Osaka)

head and the electrodeposited permalloy as a write head [2], the speed of increase in the recording density of HDD jumped from 10 times per decade to 100 times per decade. In ultra-high density recording of the future, issues such as the saturation of the write head core and the thermal relaxation of recording medium are expected to become serious. For magnetic recording media some new proposals have been made to alleviate the problem of instability. The perpendicular magnetic medium is one of the candidates, and presently it offers the possibility for solving the thermal stability [3 6]. For the write head core material, both saturation magnetic ux density (BS) and specic resistivity (z) must be increased. Recently, the permalloy with the composition of Ni45Fe55 has been in use instead of Ni80Fe20, although corrosion resistance of the latter materials is insufcient [7]. However BS and z, values

0013-4686/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 0 1 3 - 4 6 8 6 ( 0 0 ) 0 0 4 0 7 - 2

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Fig. 1. Trend of increase in recording density of hard disk drives (HDDs) during the past 15 years.

Fig. 3. Diagram showing regions of composition with low coercivity (HC B2) for CoNiFe thin lms electrodeposited from the baths containing various additive; A, saccharin bath; B, thourea bath; C, no-sulfur-containing additive (SCA) bath.

of permalloy lms (BS =0.91.0 T and z=2025 mV cm for Ni80Fe20, and BS =1.51.6T and z=4045 mV cm for Ni45Fe55) are still unsatisfactory. Many different electrodeposited lms have been reported to possess high BS values; for example, CoFe with BS =1.81.9 T [811], CoNiFe with BS =1.61.8 T [12 15]. Sputtered lms have also been reported to posses high BS value; e.g. BS =1.41.7 T for FeSiBCuNb and Fe-(Ta,Hf,Nb, etc.)(N,C,B,O) [1618], and very high BS for FeN with [1921]. As a process for fabricating merged MR head, however, an electrochemical process is preferred. This presentation reviews primarily the contribution in the area of research and development of electrodeposited soft magnetic lm for MR head of next century [22,23].

2. Soft magnetic materials

2.1. Magnetic properties of new CoNiFe lm


The composition-BS diagram for CoNiFe bulk ternary alloy published by Bozorth [24] is reproduced in Fig. 2. Many high BS materials with composition near Fe60Co40 are known, but they do not possess low HC values. Thus, it was a challenge for one to create the high BS ( \2 T) CoNiFe soft magnetic lms by electrodeposition. The diagram of Fig. 3 shows compositional regions of low HC of the CoNiFe lm which was prepared by electrodeposition. The region of BS \ 1.8 T on electrodeposited lm was found to be located in approximately the same area as that shown in Fig. 2 for the bulk material. This area is apparently determined by relative concentrations of the three elements constituting the material. It is seen from Figs. 2 and 3 that the B and C regions are located in the Co-rich area with BS \ 1.8T, whereas the A region is located in the low BS area. The baths used to generate A and B regions in Fig. 3 contain saccharin [25] and thiourea [26,27], respectively, which caused codeposition of a small amount of sulfur in the lms, whereas the bath used to form the lms in the C region does not contain such a sulfur-containing additive (hereafter designed as SCA). The composition and operating conditions of the baths used are listed in Table 1. The lms deposited in the saccharin and thiourea baths contained sulfur of 0.35 and 0.9 at.%, respectively, whereas the sulfur content of the lm from

Fig. 2. Diagram showing region of composition with high saturation magnetic ux density for bulk CoNiFe ternary alloy published by Bozorth [24].

T. Osaka / Electrochimica Acta 45 (2000) 33113321 Table 1 Basic bath composition and operating condition for electrodeposited CoNiFe soft magnetic lms Chemicals Concentration (mol dm3) 0.030.0875 0.2 0.0050.045 0.4 0.28 0.01 010 2.8 Room temp. Pt wire 320

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CoSO47H2O NiSO46H2O FeSO47H2O H3BO3 NH4Cl Na laulyl sulfate (g dm3) Sulfur containing additive (SCA)a (g dm3) Bath pH Bath temperature Counter electrode Current density (mA cm2)

a SCA; saccharin (as Nasalt) 010 g dm3; thiourea 00.06 g dm3.

no-SCA bath was less than 0.1 at.%. The sulfur analysis was initially performed by the TEMEDX and EDX methods to make relative comparison between many samples prepared under widely different conditions. The absolute sulfur contents were determined later by the conventional combustion method. It was found that the values obtained by the TEMEDX and EDX methods were approximately three times as large as those found by the combustion method. Therefore proper correction was applied to the TEMEDX values to compare absolute sulfur contents on the normalized basis. The lines indicating fccbcc phase boundary are shown in Fig. 4, in which line D for rapidly quenched ribbon was taken from Ref. [28], representing the case of no sulfur inclusion. If the mixed fccbcc phase is assumed to consist of small crystallites, low HC lm should form near the region of fccbcc phase boundaries, because the formation of small crystallites is one of the important factors leading to low HC. In fact, it has already been reported that an electrodeposited CoNiFe lm with an especially low HC value of 0.06 Oe (4.8 A m 1) contains small crystallites near the region of fccbcc phase boundaries [14]. However, CoNiFe lms with HC B2 Oe (159 A m 1) and BS \ 1.9 T or even any soft magnetic lms with HC B2 Oe (159 A m 1) and BS \2.0 T, have not been reported thus far. Fig. 5 shows bright eld images of bcc single phase, fccbcc mixed phase, and fcc single phase of the high BS CoNiFe lms. With the fccbcc mixed phase, the low HC value was obtained. From these images, it is clear that the fccbcc mixed phase is formed with ne crystal grains compared with those of bcc or fcc single phases. It is thus likely that the newly developed soft

magnetic lm can be prepared only by electrodeposition [29,30]. The mixed phase lines are clearly dependent on the trace amount of sulfur inclusion. The lm electrodeposited with no-SCA gave the fcc bcc mixed phase line in the highest BS region. It is important to note that uS of the lm to be used for fabricating the magnetic head core should be low because magnetic eld does not produce stress in such lms whose uS value is nearly equal to zero. In addition, the characteristics of uS of the electrodeposited lms are generally different from those of the lms prepared by other thin lm techniques such as sputtering and quenching. Fig. 6 shows the zero magnetostriction lines for the three electrodeposited CoNiFe lms and the quenched CoNiFe alloy [28]. The trend for the quenched alloy, which is described in Ref. [28] is quite different from that of the electrodeposited lms. The three electrodeposited lms exhibited almost the same tendency as shown in Fig. 6. The zero uS line shifts to the region of lower Fe contents with an increase in S content. Namely, the lm with low uS shifts to the higher BS region with a decrease in S content. The results show that the zero uS line of the CoNiFe lm from the bath with no-SCA is located near the low HC and high BS region. Thus, one of the most suitable lms has a composition of Co65Ni12Fe23 (at.%) with high BS (2.1 T), low HC (1.2 Oe (95 A m 1)), low uS (1.8 10 6) and usual z (21 mV cm). This lm is designated as HB-CoNiFe. It is clearly seen from in Figs. 4 and 6 that the inclusion of a small amount of sulfur in the CoNiFe lm drastically affects the formation of fcc bcc mixed phase and the location of the zero uS line.

Fig. 4. Bcc-fcc phase boundaries of electrodeposited CoNiFe thin lms deposited from the baths containing various additives; A, saccharin bath; B, thourea bath; C, no-sulfur-containing additive (SCA) bath. Line D for rapidly quenched ribbon [28] is shown comparison.

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Fig. 5. TEM bright eld images of electrodeposited CoNiFe thin lms deposited from the no-sulfur-containing additive (SCA) bath with various crystalline structures; C1, bcc structure; C2, bcc-fcc mixed structure; C3, fcc structure. THEED patterns are also shown.

2.2. Corrosion resistance of new CoNiFe lm


Corrosion resistance of CoNiFe lm was investigated in a 2.5 wt.% NaCl solution [29,31,32]. The corrosion resistance should be considered as an indication of durability of the lm material. Fig. 7 shows anodic polarization curves of the HB-CoNiFe lm, the electrodeposited CoNiFe lm prepared in the saccharin bath, and the permalloy lm electrodeposited from a bath also containing saccharin. The conventional bccCoNiFe lm had the same composition as the HBCoNiFe lm except for the inclusion of a small amount of sulfur in the former (CoNiFe, 0.3 at.% sulfur; permalloy, 0.1 at.% sulfur; HB-CoNiFe, less than 0.1 at.% sulfur). Comparison of the polarization curves for the two types of CoNiFe ternary alloy lms shows that the anodic dissolution potential (or rest potential) of the HB-CoNiFe lm, 870 mV versus SCE, is slightly more cathodic than that of the permalloy and the CoNiFe lms, 820 mV, whereas the pitting corrosion potential of the HB-CoNiFe lm is 65 mV, which is much more anodic than that of the bcc-CoNiFe lm, 420 mV (pitting corrosion potentials are indicated by dotted lines in Fig. 7). Pitting corrosion potential is more important in practical application than dissolution potential. The pitting corrosion potential of the HB-CoNiFe lm is even more anodic than that of the permalloy lm. The results show that the HB-CoNiFe lm has the most superior anti-corrosion property among the three lms tested, and that the pitting corrosion potential is strongly dependent on the very small amount of S inclusion, even although the difference in anti-corrosion property between the two CoNiFe lms with same sample composition results not only from the difference in sulfur inclusion, but also from the difference in crystal size of the lms.

3. Basic research on the effect of sulfur containing additives Since the role of the SCA is so important in providing such excellent properties to the CoNiFe lm, the basic investigation was performed to understand the mechanism of inclusion of sulfur from SCA additives [33]. The mechanism of inclusion of impurity elements in nickel lms electrodeposited from the well-known

Fig. 6. Zero magnetostriction lines for electrodeposited CoNiFe thin lms deposited from the baths containing various additives; A, saccharin bath; B, thourea bath; C, no-sulfurcontaining additive (SCA) bath. Line D for rapidly quenched ribbon [28] is shown for comparison.

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Fig. 7. Anodic polarization curves for electrodeposited soft magnetic thin lms recorded in 2.5 wt.% NaCl solution; A, 80-permalloy; B, bcc CoNiFe; C, HB-CoNiFe. The electrolyte solution was degassed by bubbling N2 for 5 min prior to use. Dotted lines show pitting corrosion potentials.

The rst attempt to observe adsorbed saccharin molecules was made by the author [33] by immersing a fresh Au(111) electrode prepared by the anneal and quench method in an aqueous 0.1 mM (18 mg dm 3) saccharin solution for 10 min, followed by rinsing the electrode thoroughly in pure water and transferring it into the STM cell containing 0.05 M HClO4. An Au(111) electrode was used because it is most commonly used for EC-STM observations. In the potential range where no faradaic current owed, only the structure of Au(111) was observed, indicating that adsorbed saccharin molecules, if any, had been removed from the electrode surface during the water rinse. Thus, the second attempt was made by adding a small amount of 0.5 mM (96 mg dm 3) saccharin directly into the STM cell containing 0.05 M HClO4 to make the nal saccharin concentration equal to approximately 50 mM (9.6 mg dm 3). The potential of the gold electrode was held at 0.75 V versus RHE. Upon injection of the saccharin

Watts bath containing saccharin, thiourea, and other additives was studied in detail during the period of the late 1950s to the 1970s [3447]. Because nickel is a major constituent of the CoNiFe alloy, and also because all three components of the alloy belong to the same group in the Periodic Table of the Elements, the interaction of the bath additives with CoNiFe can be anticipated to be similar, at least qualitatively, to that with pure Ni. In a recent research, in-situ ECSTM experiments were carried out with a single crystal Au(111) electrode on the basis of this consideration. Effects of saccharin and thiourea concentrations on the sulfur content and the coercivity of CoNiFe lms are shown in Fig. 8A and B, respectively. With saccharin as the additive, the S content was essentially invariant at 0.3 90.05 at.% between the saccharin concentrations of 2 and 10 g dm 3, where the HC value was also nearly constant at 42 92 Oe (3320 9160 A m 1). With thiourea, on the other hand, the S content increased almost linearly with its concentration between 0.005 and 0.06 g dm 3. The HC value initially decreased sharply with increasing thiourea concentration, reaching a minimum of approximately 2 Oe (160 A m 1) at the thiourea concentration of 0.0150.02 g dm 3. Further increase in thiourea concentration caused a linear increase in HC at least up to 20 Oe (1600 A m 1) at the thiourea concentration of 0.06 g dm 3. The lms obtained with saccharin are not useful as a soft magnetic lm due to higher coercivity, whereas, the use of thiourea permits the formation of CoNiFe lms of practical value [27,28].

Fig. 8. Coercivity and sulfur inclusion of electrodeposited CoNiFe thin lms deposited from the sulfur-containing additive (SCA) baths; A, saccharin bath; B, thiourea bath.

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(molecules) at the edges of tightly packed domains moved, causing clear bright spots to become unclear and vice versa. These observations indicate that saccharin molecules adsorb only weakly on the Au(111) surface. The STM observation of adsorbed thiourea was carried out under the conditions identical to those employed in the rst experiment with saccharin described above. Namely, after the Au(111) substrate was immersed in a 0.1 mM (7.6 mg dm 3) thiourea solution for 10 min, it was removed from the solution and rinsed thoroughly with pure water prior to transferring into the STM cell containing 0.05 M HClO4. Unlike saccharin, adsorbed thiourea survived the water rinse and yielded the STM images reproduced in Fig. 10A and B, which were recorded at 0.65 V versus RHE. It is seen from Fig. 10A that the Au(111) terraces separated by

Fig. 9. In-situ STM images of saccharin adlayer on Au(111) substrate in 0.05 HClO4 containing 0.05 mM (96 mg dm 3) saccharin. Applied potential, 0.75 V vs. RHE. Frame size: A, 100 100 nm; B, 30 30 nm.

solution, the image of the hexagonal atomic structure of bare Au(111) surface changed dramatically into that of adsorbed saccharin molecules, which is shown in Fig. 9A and B. Fig. 9A shows that a large number of bright spots are distributed over the entire terrace. Each bright spot is more clearly seen in the enlarged image of the area of 30 30 nm2 in Fig. 9B. From the size of each spot (ca. 0.8 nm) and the size of a saccharin molecule (see Fig. 11A), it is clear that each bright spot in the STM image corresponds to an individual saccharin molecule. It is seen that the saccharin molecules are tightly packed on the surface, but they do not form any ordered structure. Molecular defects and diffuse surroundings of the bright spots are seen especially clearly in Fig. 9B. During the imaging it was frequently seen that the spots

Fig. 10. In-situ STM images of thiourea adlayer on Au(111) substrate in 0.05 HClO4 containing 0.1 mM (9.6 mg dm 3) thiourea. Applied potential, 0.75 V vs. RHE. Frame size: A, 100 100 nm; B, 30 30 nm.

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4. Research on high CoNiFe lm From the viewpoint of the rate of data recording, a high resistivity (z) of the head core materials is required to decrease eddy-current loss. Electrodeposited soft magnetic materials with high z have not been studied as much as high BS materials, but some attempts have been made to prepare soft magnetic thin lms with high z values such as electrodeposited NiFe [49], NiFeMo [50,51], FeP [52,53], and NiFeP [54]. There is no report on soft magnetic materials satisfying condition of both high BS and high z for the write-head of the high-density magnetic recording system of the future. To develop a new soft magnetic thin lm with both high BS and high z, an attempt was made to increase the resistivity of the electrodeposited high BS CoNiFe thin lm. It was recently found that an electroless NiP lm with an extremely high z value of 5000 mV cm can be deposited from a bath containing a complexing agent having NH2 groups [55,56]. This nding led one further to an attempt to electrodeposit a the highly resistive soft magnetic lm from a bath containing an organic compound agent having NH2 groups as an additive instead of a complexing agent. With diethylenetriamine (DET) as an additive [49,54], the z value of the Ni80Fe20 permalloy lm was found to increase from 20 to 60 mV cm. It has been shown that a small amount of C incorporated in the lm from the additive of DET increases the resistivity of the lm, where the C content was determined with a combustion method. The electrodeposited CoNiFe lm made with no SCA, which exhibited higher performance as a soft magnetic lm than permalloy as described in the preceding section, was examined for the improvement of resistivity with the DET additive in the deposition bath [57]. Fig. 12 shows the dependence of BS and HC on the DET concentration in the plating bath. The metal composition of all CoNiFe lms was kept at Co56Ni13Fe31 (the deviation was less than 1 at.%). The value of BS was maintained as high as 1.9 T the DET concentration of up to 8.0 g dm 3, although it was slightly lower than 2.1 T, which is the value in the absence of DET. The value of HC was lower 2.5 Oe (180 A m 1) up to 8.0 g dm 3 of DET, but this value rapidly increased with the addition of more than 8.0 g dm 3 of DET. Fig. 13 shows the dependence of z value on DET concentration. The value of z gradually increased with DET concentration, and the lm prepared from the bath containing 20 g dm 3 of DET had a high z value of 130 mV cm. These results show that the desirable soft magnetic CoNiFe thin lms with a high z value of 90 mV cm can be deposited from the new bath containing 8.0 g dm 3 of DET as an additive.

Fig. 11. Schematic drawings of molecular structures; A, saccharin; B, thiourea.

monatomic steps 0.24 nm in height were covered with many string-shaped substances. Those short pieces of strings are seen more clearly at an expanded scale in Fig. 10B. Comparison of the dimensions of each piece of string with the size of a single thiourea molecule, shown in Fig. 11B, seems to indicate that a single piece of string represents a polymeric molecule consisting of several, linearly combined molecules of thiourea. Although the string-shaped polymer molecules are closely packed, forming a layer, no ordered structure or regularity in molecular orientation was found with respect to the structure of the Au(111) surface. These features were observed consistently in the potential range of 0.40.8 V versus RHE, suggesting that thiourea molecules are strongly adsorbed on Au(111) surface. Furthermore, Fig. 10A and B show the presence of many pits on the surface. Such pits were not found on clean Au(111) surfaces. The depth of these pits is almost equal to the height of monoatomic steps existing on the Au(111) surface, that is 0.24 nm. Careful observation of the inside of the pits revealed that the string-shaped material existed also at the bottom of the pits, as can be seen in Fig. 10B. In view of the known high stability of soluble Au(I)thiourea complex, Au(CS(NH2))+ [48], the pit formation is likely to be a 2 result of the dissolution of gold to form this complex species. To compare the size of saccharin and thiourea molecules, the schematic drawings of molecular structures of the two molecules are shown in Fig. 11. From the STM images shown results in Figs. 9 and 10, it its clear that the additives of saccharin and thiourea act quite differently on the Au(111) electrode surface. It is concluded that the saccharin adsorbs weakly and only physically on the Au(111) surface, whereas thiourea adsorbs strongly to form chemisorbed polymerized thiourea molecules.

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Fig. 12. Magnetic properties of electrodeposited CoNiFe thin lms as a function of diethylenetriamine (DET) concentration.

Fig. 14. Carbon content of electrodeposited CoNiFe thin lms as a function of diethylenetriamine (DET) concentration.

In order to clarify the mechanism of the increase in z value, the crystal structure of the lms prepared from different baths with or without DET additive was analyzed. The X-ray diffraction proles of bcc-Fe disappeared as the DET concentration was increased. It was thus conrmed that the crystallinity of the lm prepared with DET was lower than that prepared without DET additive. In addition, the lm compositions of the lms prepared from different baths with or without DET additive were analyzed. Fig. 14 shows the dependence of carbon content on the DET additive concentration. The CoNiFe thin lm prepared without DET contained a very small amount of carbon, i.e. less than 0.1 at.%. The carbon content gradually increased as the DET concentration was increased, and the lm prepared with 20 g dm 3 of DET contained 0.3 at.% carbon, which

was three times as large as the carbon content of the lm prepared without DET. The desirable soft magnetic CoNiFe lm with a high z value of 90 mV cm prepared from the bath with 8.0 g dm 3 of DET contained 0.24 at.% carbon. Therefore, it is considered that the increase of z value is attributable to the change in microstructure and the effect of impurity scattering resulting from the co-deposition of carbon in the lm. Properties of the various electrodeposited CoNiFe lms are listed in Table 2. As a result of the frequency dependence of permeability of CoNiFe lms with both low and high resistivity, the loss at higher frequencies was clearly diminished with an increase in z [57]. Thus, the desirable property of the new CoNiFe thin lm is attributable to the decrease of eddy-current loss resulting from the increased z value. 5. Application of new materials to fabrication of GMR head Fig. 15 shows an SEM image and a schematic of a GMR head with the high BS CoNiFe lm as the writing-head core material [58,59]. The core was fabricated with a 0.7 mm thick high BS CoNiFe lm and the thicker permalloy lms of 2.3 mm.
Table 2 Magnetic properties and resistivity of electrodeposited CoNiFe soft magnetic thin lms with high BS and/or high z CoNiFe DET (g dm3) BS (T) z (mV cm) HC (Oe) 0 2.1 25 1.2 CoNiFe+DET 8 1.9 90 2.3 20 1.7 130 5

Fig. 13. Resistivity of electrodeposited CoNiFe thin lms as a function of diethylenetriamine (DET) concentration.

T. Osaka / Electrochimica Acta 45 (2000) 33113321 Table 3 Write head dimensions and read head element Type I CoNiFe locationa Write track widthb (mm) Write gap length (mm) Read element
a

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Type II P2 1.51.8 0.30 AMRc

Type III P1 and P2 1.11.2 0.20 GMRd

None 1.72.5 0.35 AMRc

P1 is for the bottom pole, and P2 is for the top pole. Read track width is smaller than write track width by 0.20.4 mm. c AMR is MR element using anisotropy magnet-resistive effect. d GMR is GMR element using giant magnet-resistive effect.
b

Fig. 15. SEM image and schematic illustration of GMR head structure.

25 nm. A write current of 35 mA was enough to write in the media with an HC of 7.0 kOe (560 kA m 1). This is the champion data to be recorded in the highest coercivity medium in the world. Fig. 17 shows the magnetic force microscopy (MFM) image of recording patterns in 7000 Oe medium. The magnetic patterns are clearly formed by the new type head using HB CoNiFe lm (Type III).

First the effect of CoNiFe location on overwrite performance was examined. In this experiment, the ying height was about 35 nm, and the estimated magnetic spacing was 58 nm (i.e. spacing between the surface of magnetic recording layer, not of medium surface, and the head surface). The write frequency for the overwrite measurement was 60 MHz/10 MHz (HF/ LF). The corresponding linear density for HF was 200 kFCI. The write current was 35 mA0 p for Types I and II, and 50 mA0 p for Type III. The head properties are shown in Table 3. An overwrite requirement ( \ 26 dB) limits the maximum medium coercivity that one can use. For Type I head, it was 3.0 kOe (240 kA m 1). For Type II head, it was 3.5 kOe (280 kA m 1). Furthermore, Type III head wrote well in the media with an HC as high as 5.0 kOe (400 kA m 1). The effect of the ying height is summarized in Fig. 16. By reducing the ying height to 25 nm (estimated magnetic spacing is 47 nm), the overwrite limit was increased to 7.0 kOe (560 kA m 1) for Type III head. The calculated maximum write eld of a well head, when the magnetic spacing was 47 nm, was about 10 kOe (800 kA m 1). The write saturation curves of overwrite for Type III head are also shown in Fig. 16. The ying height was

Fig. 16. Overwrite characteristics of writing head with or without high BS CoNiFe lm; (1) without CoNiFe, ying height=35 nm; (2) without CoNiFe, ying height=25 nm, (3): with CoNiFe, ying height =35 nm; (4) with CoNiFe, ying height=25 nm. Recording performance was as follows; gap length, 0.20 mm; track width, 1.1 mm; recording density, 110 kBPI, 33 kFRPI signal overwritten with 200 kFRPI signal. Dotted line shows the value of overwrite requirement ( \26 dB).

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T. Osaka / Electrochimica Acta 45 (2000) 33113321 [4] N. Honda, K. Ouchi, Digest of The Magnetic Recording Conference, A3 (1999). [5] J. Hokkyo, T. Onoue, N. Miyamoto, T. Homma, T. Osaka, J. Magn. Soc. Jpn. 22 (1997) 525. [6] T. Onoue, A. Takizawa, T. Hirayama, M. Ikeda, T. Homma, J. Hokkyo, T. Osaka, H. Sakai, T. Yoshikawa, J. Magn. Soc. Jpn. 23 (1999) 977. [7] N. Robertson, H.L. Hu, C. Tsang, IEEE Trans. Magn. 33 (1997) 2818. [8] S.H. Liao, IEEE Trans. Magn. MAG-23 (1987) 2981. [9] J.W. Chang, P.C. Andricacos, B. Petek, L.T. Romankiw, Proc. of the 2nd Intern. Symp. on Magnetic Materials, Processes and Devices, Electrochem. Soc. PV92-10 (1992) 275. [10] O. Shinoura, A. Kamijima, J. Surf. Finish. Soc. Jpn. 44 (1993) 1114. [11] Y. Hoshi, M. Naoe, J. Magn. Soc. Jpn. 10 (1986) 315. [12] N.C. Anderson, R.B. Chesnutt (IBM), U.S. Patent, 4,661,216, 1987. [13] Y. Omata, S. Mitani, T. Taniguchi, S. Nakagawa, J. Magn. Soc. Jpn. 14 (1990) 111. [14] O. Shinoura, A. Kamijima, Y. Narumiya, J. Magn. Soc. Jpn. 18 (1994) 277. [15] T. Okamoto, H. Yamada, S. Sugawara, S. Ishio, J. Magn. Soc. Jpn. 19 (1995) 445. [16] K. Yoshizawa, K. Yamauti, J. Jpn. Inst. Mat. 53 (1989) 241. [17] N. Ishiwata, C. Wakabayashi, H. Urai, J. Appl. Phys. 69 (1991) 5616. [18] N. Hasegawa, M. Satio, A. Kojima, A. Makino, Y. Misaki, T. Watanabe, J. Magn. Soc. Jpn. 14 (1990) 319. [19] M. Takahashi, H. Shoji, M. Abe, H. Komaba, T. Wakiyama, J. Magn. Soc. Jpn. 14 (1990) 283. [20] T. Ogura, M. Kume, K. Kuroki, J. Magn. Soc. Jpn. 18 (S1) (1994) 195. [21] T. Suzuki, K. Takano, K. Nakamura, J. Magn. Soc. Jpn. 19 (S1) (1995) 38. [22] T. Osaka, Electrochim. Acta 44 (1999) 3885. [23] T. Osaka, T. Momma, T. Yokoshima, Electrochemistry 67 (1999) 894. [24] R.M. Bozorth, Ferromagnetism, vol. V, D. Van Nostrand Company, New York, 1951, p. 160. [25] A. Nakamura, M. Takai, K. Hayashi, T. Osaka, J. Surf. Finsh. Soc. Jpn. 47 (1996) 934. [26] M. Takai, K. Hayashi, M. Aoyagi, T. Osaka, J. Electrochem. Soc. 144 (1997) L203. [27] M. Takai, K. Hayashi, M. Aoyagi, T. Osaka, J. Magn. Soc. Jpn. 21-S2 (1997) 443. [28] S. Fujimoto, F. Sato, T. Miyazaki, J. Magn. Soc. Jpn. 20 (1996) 477. [29] T. Osaka, M. Takai, K. Hayashi, K. Ohashi, M. Saito, K. Yamada, Nature 387 (1998) 796. [30] T. Osaka, M. Takai, K. Hayashi, Y. Sogawa, K. Ohashi, Y. Yasue, M. Saito, K. Yamada, IEEE Trans. Magn. 34 (1998) 1632. [31] T. Osaka, M. Takai, Y. Sogawa, T. Momma, K. Ohashi, M. Saito, K. Yamada, J. Electrochem. Soc. 146 (1999) 2092. [32] M. Saito, K. Yamada, K. Ohashi, Y. Yasue, Y. Sogawa, T. Osaka, J. Electrochem. Soc. 146 (1999) 2845.

Fig. 17. Magnetic force microscopy (MFM) image of recording pattern detained by writing head with CoNiFe lm. The value of coercivity of the medium was 7000 Oe, and recording performance was as follows: gap length, 0.20 mm; track width, 1.1 mm; recording density, 110 kBPI.

6. Conclusion The recent progress of research and development on new soft magnetic lms was reviewed for the authors award lecture (1999 Pergamon Gold Medal). New soft magnetic lms of CoNiFe for magnetic recording of the next century were fabricated with an electrodeposition technique. The new CoNiFe soft magnetic lm with high BS (=2.02.1 T) was created by controlling the inclusion of a very small amount of sulfur in the lm. The most suitable lm of HB-CoNiFe group possesses a very ne crystalline structure with 1015 nm in diameter of fccbcc mixed phase near the zero uS line. Corrosion properties of the lm are nearly identical to those of the plated 80-permalloy lm. The GMR head fabricated with the CoNiFe lm demonstrated superior performances leading to a breakthrough for materializing ultra high-density magnetic recording.

Acknowledgements The author would like to thank deeply to his colleagues and students at Applied Physical Chemistry Laboratory, Waseda University, for their contributions, without which we could not succeed in reaching the target described in this review. Especially, Dr Madoka Takai, Mr Akiyoshi Nakamura, Mr Katsuyoshi Hayashi and Mr Tokihiko Yokoshima were the key persons in this successful project. Dr Keishi Ohashi and his group of NEC Corporation also contributed greatly to the development of the lm and to the transfer of the basic results of research to the application.

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