J Mater Sci: Mater Electron (2011) 22:614625 DOI 10.

1007/s10854-010-0186-8

Formation and transformation of metastable phases during electrodeposition and annealing of cobaltiron alloy lms
B. Crozier Q. Liu D. G. Ivey

Received: 10 June 2010 / Accepted: 31 July 2010 / Published online: 13 August 2010 Springer Science+Business Media, LLC 2010

Abstract During the electrodeposition of CoFe alloy lms from a CoSO47H2O-FeSO47H2O bath, the formation of metastable phases, such as a complex cubic CoFe phase isostructural to a-Mn and the HCP e-Co/Fe and X-Co/Fe phases, appears to be related to the incorporation of metal hydroxide/oxide precipitates into the plated alloy lms. In the absence of the incorporated precipitates, the plated lms are the equilibrium a-Fe solid solution BCC phase. Thus, the addition of stabilizing reagents (such as ammonium citrate), and/or a lowering of solution pH, prevents the formation of the precipitates and promotes the formation of the BCC phase. On the other hand, increasing temperature causes the formation of metastable phases, possibly through the weakening of the stabilizing effect of the ammonium citrate, or the promotion of the formation of metal hydroxides/oxides precipitates. The BCC phase has higher saturation magnetic ux densities and lower coercivities than the metastable phases. Annealing of the lms transforms the metastable phases, if present, into the BCC phase, leading to a decrease in the coercivity. An increase in the magnetic ux density after annealing is, however, not observed, possibly due to the cracking or delamination of the lms as a result of annealing. Cracking and delamination make the determination of the lm volume, which is required for magnetic ux density calculation, questionable.

1 Introduction Electrodeposition is an economical method used to fabricate soft magnetic lms, e.g., CoFe, CoFeNi, CoFeB, CoFeCr, for utilization in applications such as write heads for hard disk drives [15]. Focusing on the CoFe system, high saturation ux densities (2.22.4 T) and low coercivities (\10 Oe) can be achieved through careful control of the electrodeposition process. In particular, very small grain sizes (\20 nm) have been shown to signicantly lower the coercivities of magnetic thin lms according to a D6 dependence, where D is the grain size [6, 7]. For nano-sized grains then, a small change in grain size results in a large change in coercivity. One way of achieving these grain sizes is through competitive growth of two deposit phases [810]. These are typically the BCC and FCC solid solution phases, a-Fe (Im3m space group) and c-Fe/a-Co (Fm3m space group). The binary phase diagram for the CoFe system (Fig. 1) shows 4 stable phases in the temperature range of 5001,700 C. These include the aforementioned a-Fe and c-Fe/a-Co, as well as the ordered a phase, which has a CsCl-type structure (Pm3m space group) and essentially resembles the a-Fe phase except that Co and Fe are ordered on the lattice positions. The d-Fe phase is a second BCC phase (Im3m space group) which exists at Fe-rich compositions at high temperatures close to the melting temperature. A fth equilibrium phase exists at temperatures below those shown in Fig. 1 (\422 C), i.e., HCP e-Co (space group P63/mmc). The binary phase diagram gives a good indication of the phases that might be expected in CoFe thin lms at a particular composition. Electrodeposition, however, often produces lms that are composed of phases which are not thermodynamically stable [12] for the compositions and

B. Crozier Q. Liu D. G. Ivey (&) Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 2V4, Canada e-mail: doug.ivey@ualberta.ca

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orientation forming a banded structure. The bands are aligned perpendicular to the substrate surface and consist of similarly oriented grains (520 nm in size). The a-Mn type phase transforms to the BCC solid solution phase (a-Fe) upon annealing at temperatures exceeding 178 C. The transformation to the BCC phase begins at the seed layer/deposit interface. The aim of this work is to explore in more detail the formation of the a-Mn type metastable phase during electrodeposition of CoFe thin lms from solutions consisting of sulfate salts. In particular, the effects of solution chemistry and electrodeposition conditions (temperature, pH and current density) are examined. X-ray diffraction (XRD) and electron microscopic techniques are used to study the microstructure, which is correlated to the magnetic properties of the deposits.
Fig. 1 CoFe equilibrium phase diagram [11]

temperatures shown on the phase diagram. For instance, although stable at low temperatures and over a wide composition range (*2575 at% Fe) according to the phase diagram (Fig. 1), the a0 phase is almost never observed in electrodeposited thin-lms [9]. Also, the range in composition over which the FCC and BCC phases can be deposited often conicts with the regions shown in Fig. 1 [9, 13]. In fact, electrodeposition often produces metastable phases [12]. These phases arise due to kinetic effects during the electrodeposition process, as well as to the incorporation of impurities in the deposits [12, 14]. One metastable phase was recently reported by our group [15, 16] in electrodeposits from solutions containing Co and Fe sulphate salts and either tribasic or dibasic ammonium citrate. In these solutions, ammonium citrate was added as a stabilizing agent, to delay precipitate formation in the solutions, allowing the plating solutions to be used at their natural pH values. This removes the need for lowering the solution pH, thereby reducing hydrogen evolution which can lead to void formation in the deposits [10]. The metastable phase formed over a range of Co/Fe compositions (3080 at% Co) and at elevated electrolyte temperatures (4060 C). It was identied as a complex cubic phase (58 atoms per unit cell) which is isostructural to a-Mn (space group I43m). To the authors knowledge these citations are the rst reports of the a-Mn type phase forming in the CoFe system through electrodeposition. The a-Mn type phase has previously been reported in ironcobalt alloys through precipitation reactions [1721] and vapour deposition [19]. Phases with similar structures were also formed in FeCr and FeNiCr alloys through magnetron sputtering [2224]. Crozier et al [16] have shown, through transmission electron microscopy (TEM), that the a-Mn type phase exhibits some degree of preferred

2 Experimental methods Electrodeposition was carried out in a simple polypropylene electroplating cell, with the anode and cathode mounted vertically. The cathode consisted of a diced section of a Ti (100 nm)/Au (500 nm) metalized (100) oriented, single crystal Si wafer, and a diced section of a Ti (75 nm)/Pt (200 nm) metallized Si wafer was used as the anode. The metals were deposited by magnetron sputtering onto the Si substrates; the Ti acted as the adhesion layer upon which the Au or Pt was deposited. Patterned photoresist was applied to the cathode surface to dene the plating area. A 50 X standard resistor was placed in series with the plating bath across which an oscilloscope was connected and used to monitor the waveform in the circuit and to corroborate the current output of the power supply. Current was supplied using a Dynatronix, Inc. (Model DuPR10-.1-.3) power supply. The composition and pH of the standard electroplating solution are shown in Table 1. For each deposit, fresh solution was used and the pH of the solution was not adjusted from its natural value of *3.5. The standard plating conditions consisted of an average current density of 15 mA/cm2, pulsed with a 10 ms duty cycle of 6 ms ontime followed by 4 ms off-time. The parameters were chosen based on previous work where the same parameters gave optimal soft magnetic properties for a similar solution [10]. This solution and these plating parameters were used for all deposits unless otherwise specied. Select deposits were annealed in a tube furnace in a reducing atmosphere (5% H2 in N2) at three different temperatures: *174, 225, and 390 C. These temperatures were chosen primarily because they allow for the observation of partially and fully transformed deposits

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616 Table 1 Composition of standard electroplating solution Reagent CoSO47H2O FeSO47H2O H3BO4 Sodium lauryl sulphate Dibasic ammonium citrate pH Concentration (mol/L) 0.12 0.048 0.4 0.01 g/L 4.65 g/L 3.5

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condition were measured and the results averaged; the tests were done at 300 K.

3 Results and discussion 3.1 Effect of plating temperature on CoFe thin lms 3.1.1 Composition of CoFe deposits The molar ratio of Co:Fe of the solution was 2.5:1, which should result in deposits with compositions of *71 at% Co (29 at% Fe) assuming non-preferential plating by either species. EDX analysis was used to determine the composition of electrodeposited CoFe thin lms (Table 2). As can be seen, at room temperature, Fe is preferentially deposited, relative to the solution composition, at the expense of Co. Iron has a lower reduction potential than Co. Therefore, the results indicate slightly anomalous plating behaviour for the plating solution at room temperature. This behaviour is well established in the literature [2, 8, 15, 25] and is thought to be the result of an inhibiting effect of Fe(II) on the nucleation and growth of Co on the cathode surface [25]. When the plating temperature is increased to 40 C the composition of the deposits closely reects the solution composition, while at 60 C the deposits become Co-rich. These results agree with the behaviour observed by other researchers using similar plating solutions [15, 26]. EDX measurements taken from cross section TEM samples (not shown here) indicate that the composition is uniform through the deposit thickness. The oxygen content of the deposits was determined using XPS, with values ranging from 3 to 5 at% O. Oxygen is likely incorporated as oxide or hydroxide precipitates, as discussed in more detail later in the TEM analysis. Oxide precipitates are either non-magnetic or weakly magnetic, so their incorporation into the deposits should result in lower saturation magnetic ux density values. The incorporation of oxide precipitates may also affect deposit structure and other deposit properties such as resistivity, hardness and strength by imposing lattice strain in the deposits, and could compromise the integrity of the deposits.

composed of the a-Mn-type phase. The deposits were heated to the desired temperature, over a 20 min time interval, and held for 4 h before furnace cooling to room temperature. Phase analysis for the deposits was done using X-ray diffraction (XRD) and electron diffraction. XRD was done using a Rigaku Rotaex thin lm XRD system, with a rotating anode. An incident beam angle of 2 was used with a scanning rate of 2 per minute. Based on instrument availability, some experiments were conducted using a Co anode and others using a Cu anode. For the Co anode, a voltage of 40 mV and a current of 160 mA were used; for the Cu anode, a voltage of 40 mV and a current of 100 mA were used. The XRD patterns were analyzed using Jade Version 5.0 XRD software. Selected area electron diffraction (SAD) patterns were obtained using a JEOL 2010 transmission electron microscope (TEM) operated at 200 kV. Deposit morphology was examined in plan view and cross section orientations using a Hitachi S-2700 scanning electron microscope (SEM), operated at 20 kV and equipped with secondary electron (SE), back-scattered (BSE) and energy dispersive X-ray (EDX) detectors. A working distance of 15 mm was used for EDX analysis. Higher resolution images were obtained with the JEOL 2010 TEM in both bright eld (BF) and dark eld (DF) modes. Cross section samples for TEM analysis were prepared using a standard mechanical polishing, dimpling and ion milling procedure. Thickness measurements were obtained using a Tencor AS-200 prolometer. Measurements were averaged from 5 different, evenly spaced points across the deposit surface using the bare substrate as the reference point. The oxygen content of deposits was determined by X-ray photoelectron spectroscopy (XPS), using a Kratos Axis 165 XPS system with a monochromatic aluminum Ka X-ray source (1,486.6 eV) operated at 210 W. Prior to measurement, deposit surfaces were sputtered with argon to remove any surface oxide lms. Magnetic property measurements were obtained using a super quantum interference device (SQUID) magnetometer (Model MPMS XL-7). Three different samples for each

Table 2 Composition of CoFe thin lms plated at various temperatures Plating temperature 20 C 40 C 60 C Co content (%) 68.3 1.0 71.6 1.0 75.7 1.0 Fe content (%) 31.7 1.0 28.4 1.0 24.3 1.0

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3.1.2 Morphology of CoFe deposits SEM SE micrographs of the surfaces and cross-sections of electrodeposited CoFe lms from dibasic ammonium citrate stabilized plating solutions at various temperatures are shown in Fig. 2. The surfaces of the deposits are generally quite smooth, with small nodules which become ner as the plating temperature is increased. Although the nodules are similar to grains in appearance, TEM analysis indicates that the actual grain size is orders of magnitude smaller than the nodule sizes. The cross-sections images show that the deposits are uniform and compact with thicknesses that do not vary appreciably with plating temperature (1.70 0.07 lm). Cracks were observed in many of the deposits plated at lower temperatures, likely a result of stress relief. Increasing the temperature is known to reduce stress in electrodeposited alloys and has often been attributed to a reduction in the overpotential for deposition of metallic species [27]. A lowering of the overpotential permits the metal cations to migrate to the cathode surface more easily

and allows the opportunity for ad-atoms to migrate to stable kink sites. In addition, a lower overpotential discourages the reduction of hydrogen at the cathode, which has also been shown to increase the residual stresses in electroplated lms [28]. 3.1.3 Phase analysis The effect of electrodeposition temperature on the phases formed in the CoFe thin lms was analyzed using XRD (Fig. 3). The CoFe BCC solid solution phase (a-Fe type) is formed at 20 C, which is as expected based on the CoFe phase diagram (Fig. 1) and is consistent with the phase structure observed by other researchers for similar electrodeposited CoFe thin lms [8, 9, 13]. The FCC solid solution phase (c-Fe/a-Co), which is stable at elevated temperatures ([900 C) or higher Co concentrations ([90 at %), was not detected in any samples. This phase was reported, however, for similar solutions with tribasic ammonium citrate, instead of dibasic ammonium citrate, by Zhang et al. [10]. As the plating temperature is increased to

Fig. 2 SEM SE micrographs of CoFe deposits, in plan view and cross section orientations, plated using the standard solution (Table 1) and plating conditions (15 mA/cm2 for 9 min) at various temperatures

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formation of the a-Mn type phase is temperature dependent, and not composition dependent, as the a-Mn type formed at 40 and 60 C in their deposits containing 6085% Co. The deposits reported here fall all within this composition range (Table 2), but no a-Mn type phase formed at 20 C, consistent with the results of Zhou et al. [15].

3.2 CoFe deposits from plating solutions without ammonium citrate

between 30 and 40 C, the a-Mn type phase begins to be codeposited along with the equilibrium BCC solid solution phase. When the temperature is increased further, the proportion of the a-Mn type phase gradually increases until it eventually replaces the BCC solid solution phase at some temperature between 50 and 60 C. Based on the peak positions in the XRD patterns, the lattice parameters for the deposit phases were calculated and are tabulated in Table 3. Higher deposit Co contents led to a small increase in the lattice parameter for the a-Mn type phase. This is to be expected due to the slightly larger atomic radius of the Co atoms [29]. The lattice parameter for the BCC solid solution, however, slightly decreases when the deposit Co content is increased. This may indicate a slight enrichment of Co in the a-Mn type phase relative to the BCC solid solution phase when the two phases are codeposited. This would cause the BCC solid solution phase to be slightly Fe-rich in comparison to the overall deposit composition and would result in a reduction in its lattice parameter. The effect, however, is quite small and the extremely ne grain size and dispersed nature of the phases in the deposits makes this hypothesis difcult to corroborate. As established above, elevated plating bath temperatures result in elevated deposit Co contents. An obvious question is whether the appearance of the a-Mn type phase is the result of higher Co contents in the deposits or the increase in plating temperature. According to Zhou et al. [15], the

In order to determine if the ammonium citrate is responsible for the formation of the a-Mn type phase, deposits were prepared from solutions in which citrate was omitted. The pH of the solution was adjusted to *3.5 which is consistent with the natural pH of the dibasic ammonium citrate stabilized solution. XRD patterns from deposits produced at various temperatures from the citrate-free solutions are shown in Fig. 4. At room temperature the a-Mn type phase is the dominant phase and the BCC solid solution phase is completely absent from the pattern. In addition to the a-Mn type phase, two non-equilibrium HCP CoFe phases were detected: e-Co/Fe (space group: P63/ mmc) and X-Co/Fe (space group: P6/mmm). As the plating temperature is increased above room temperature, the a-Mn type phase is replaced by the other phases until only residual amounts remain in deposits plated at 60 C. Three additional peaks were detected in the 60 C sample (at *39.2, 52 and 59), which could not be indexed to any known CoFe phases. A reasonable match to b-FeO(OH) (I4/m space group and also known as aka ganeite) was made, however. The two hexagonal phases were also identied in CoFe lms deposited at elevated temperatures by Zhou et al [30] when tribasic ammonium citrate was used in sulfate solutions (natural solution pH of 4.8). The e-Co/Fe phase was favored at intermediate temperatures (40 C), while X-Co/ Fe was favored at 60 C. The possible presence of b-FeO(OH) suggests that precipitates may have formed in solution and were incorporated into the deposits, particularly at elevated temperatures (60 C). Deposit oxygen contents, obtained using XPS analysis, were in the 56 at% O range (slightly higher

Table 3 Lattice parameters for electrodeposited phases Plating temperature (C) 20 40 60 Deposit Co content (%) 68.3 71.6 75.7 Deposit Fe content (%) 31.7 28.4 24.3 a-Mn type a (nm) 0.8697 0.0007 0.8708 0.0007 BCC solid solution a (nm) 0.2842 0.0001 0.2837 0.0005

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Fig. 4 XRD patterns from CoFe deposits obtained using citrate-free plating solution under standard plating conditions at various temperatures: a 20 C; b 40 C; c 60 C

Fig. 6 XRD patterns for CoFe deposits plated from the standard plating solution (without dibasic ammonium citrate) with the pH adjusted to 2.3: a 20 C; b 60 C

at 60 C), which are higher than those for deposits plated from solutions with dibasic ammonium citrate (35 at% O). 3.3 Effect of pH on CoFe deposition When the pH of the dibasic ammonium citrate stabilized solutions and the citrate-free solutions is reduced to 2.3 (the pH suggested by Osaka et. al. [3] to avoid the formation of precipitates in their solution), the equilibrium BCC solid solution phase is the only phase deposited at all temperatures, as shown in Figs. 5 and 6. The absence of the a-Mn type phase, even at elevated temperatures, in either of the solutions indicates that deposition of the phase is strongly pH dependent. The foregoing descriptions show that the presence of ammonium citrate in the plating solution is not the reason for the formation of the a-Mn type phase in the deposited CoFe lms. On the contrary, the presence of dibasic ammonium citrate appears to hinder its formation at low temperatures in favor of the BCC solid solution. Increased plating temperatures (C40 C), however, promote the deposition of the a-Mn type phase in the ammonium citrate

Fig. 5 XRD patterns for CoFe deposits plated from the standard plating solution (with dibasic ammonium citrate) with the pH adjusted to 2.3: a 20 C; b 40 C; c 60 C

stabilized plating solution, as well as other non-equilibrium phases (e-Co/Fe and X-Co/Fe) in the citrate-free solution. The formation of the a-Mn type phase structure in alloy systems has previously been attributed to the incorporation of large impurities (such as the Fe-oxides in this work) in thin lm deposits [22]. This case is not unique; the presence of dispersed impurities has been shown to lead to the formation of metastable phases in many thin-lm systems [14, 31, 32]. It is postulated that the formation of metastable phases is caused by localized distortions in the crystal lattice, which result from incorporated impurities. The distortions interfere with the electrocrystallization process and in doing so prevent the formation of equilibrium phases [14]. Since dibasic ammonium citrate both stabilizes the solution and suppresses the formation of the metastable a-Mn type phase, it seems reasonable that under these conditions metal-citrate complex ions were formed, which suppressed the formation of metal hydroxide/oxide precipitates and reduced the incorporation of these impurities in the deposited lms. As the bath temperature is increased, however, the ammonium citrate may no longer be able to prevent the formation and resultant incorporation of precipitates into the deposits, which leads to the formation of the a-Mn type phase. Since the citrate-free plating solution had no complexing agents, the a-Mn type phase was deposited even at 20 C. As the temperature is increased, the incorporation of precipitates (b-FeO(OH)) also increases. The additional precipitates may have contributed to the formation of the non-equilibrium hexagonal phases in citrate-free baths. The importance of pH on the deposition of metastable phases is shown by the inability to form any phase other than the equilibrium BCC solid solution, regardless of temperature, when the pH of both the dibasic ammonium citrate stabilized and the citrate-free plating solutions was adjusted to 2.3. This may be due to the reduced concentration (activity) of hydroxyl ions in solution at the low pH values, which prevents the formation of Fe hydroxide/ oxide precipitates.

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3.4 Effect of current density on CoFe deposits XRD patterns obtained from CoFe deposits plated at various temperatures and current densities are shown in Fig. 7. The current density does not affect the type of phases deposited at 20 and 60 C. Only the a-Mn type phase is formed at 60 C and only the BCC solid solution phase is formed at 20 C. These temperatures represent extremes in terms of a-Mn type phase and BCC solid solution phase formation and are, therefore, less susceptible to the inuences of current density. Based on the relative peak heights for the deposits plated at 40 C, however, there is a noticeable tendency to form more BCC solid solution phase, rather than the a-Mn type phase, as the plating current density is increased. High current densities are usually favorable for the formation of metastable phases as the correspondingly higher applied potential provides additional energy for the formation of phases that would normally be unstable [33, 34]. High current densities also lead to the formation of smaller grains and to hydrogen evolution, both of which have been shown to cause the formation of metastable phases [31]. The opposite trend is observed here, as a higher current density promotes the formation of the equilibrium BCC solid solution phase. As such, the formation of the a-Mn type phase must be due to reasons other than high overpotential, small grain size or hydrogen evolution. The work here shows that the formation of the a-Mn type phase is associated with the formation and incorporation of oxide precipitate particles into the deposits. It is unclear, however, how higher current densities would prevent the formation or integration of precipitates into deposits or if the precipitate content of lms deposited at higher current densities is any lower than that deposited at low current densities. Further work is needed to determine

the reason that high current densities favor BCC solid solution phase formation. 3.5 Annealing of CoFe deposits 3.5.1 Deposit morphology The samples electrodeposited from the standard solution, i.e., ammonium citrate and natural pH of 3.5, were annealed at temperatures as high as 390 C. Prior to annealing, the surfaces of the CoFe deposits were typically at and smooth. After annealing, however, the deposits exhibited signicant cracking. Optical micrographs from CoFe deposits after annealing at various temperatures are shown in Fig. 8. The cracks became prominent features on the deposits surfaces after annealing at 174 C for deposits plated at all temperatures. As the annealing temperature was increased, the amount of cracking became more severe until at 390 C the surface was not only covered in cracks but large areas of material adjacent to the cracks had delaminated. The cracking was particularly severe for the single phase deposits plated at 20 (BCC solid solution) and 60 C (a-Mn type phase). When the deposits were annealed, the thermal stresses due to the differential expansion of the deposits and substrates may have led to the cracking. The coefcients of thermal expansion for Au, Si and a bulk CoFe alloy of similar composition to the ones studied here are 14.2 lm/(m-C), 5.0 [35] and 8.1 lm/(m-C) [36], respectively. Gold will expand much more than either Si or the CoFe alloy upon heating. Since Au is adjacent to both the CoFe alloy and the Si substrate, via a thin Ti adhesion layer, thermal expansion as a source of the cracking is plausible. 3.5.2 Phase analysis of annealed CoFe deposits The effects of annealing temperature on the phase structure of deposits plated at 20 C, 40 and 60 C are shown in Figs. 9, 10 and 11. For the sample deposited at 20 C (Fig. 9), there is no change in the phases present, i.e., the BCC solid solution phase is maintained throughout the annealing process. There is a noticeable narrowing of the peaks as the annealing temperature is increased, which corresponds to coarsening of the grains. For the samples plated at 40 C (Fig. 10), the a-Mn type phase transforms to the BCC solid solution phase when annealed at temperatures C174 C. This agrees with the ndings of Jay et al. [20] who found similar transformation at temperatures above 160 C. At 174 C, the a-Mn type phase has been mostly replaced by the BCC solid solution, while at 225 C the transformation is complete after 4 h of annealing. At higher temperatures there is also narrowing of the peaks, indicating coarsening of the grain structure.

Fig. 7 XRD patterns showing the effects of current density on phase deposition using the standard plating solution and plating at: a 20 C; b 40 C; c 60 C

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J Mater Sci: Mater Electron (2011) 22:614625 Fig. 8 Optical micrographs of the surfaces of CoFe deposits after annealing at various temperatures

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Fig. 9 XRD patterns for CoFe deposits plated at 20 C using standard plating conditions, which were subsequently annealed: a as deposited; b annealed at 174 C; c annealed at 225 C; d annealed at 390 C

Fig. 10 XRD patterns for CoFe deposits plated at 40 C using standard plating conditions, which were subsequently annealed: a as deposited; b annealed at 174 C; c annealed at 225 C; d annealed at 390 C

For the deposits plated at 60 C (Fig. 11), the transformation of the a-Mn type phase to the BCC solid solution phase has begun at 174 C and the transformation is complete at 225 C. An interesting feature is the absence of the (200) peak for the BCC solid solution, which is indicative of texturing. The (200) peak for the BCC solid

solution phase is present in the deposits obtained at 20 and 40 C, even after annealing. It is, therefore, likely that the preferred orientation was transferred to the BCC solid solution phase during annealing and transformation. The a-Mn type phase has a (110) texture (parallel to the surface), which is preserved as a (110) preferred orientation

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3.6 Magnetic properties of CoFe thin lms Saturation ux densities (Bs) for as-deposited and annealed CoFe lms are shown in Fig. 13. The highest saturation ux densities (average value of 2.2 T) were obtained for as-plated and unannealed deposits. Unannealed deposits plated at 40 and 60 C had lower saturation ux densities (1.81.9 T), which can be attributed to their lower Fe levels and the presence of the a-Mn type phase. Upon annealing there was a general trend for decreasing saturation ux density. The decrease in Bs on annealing for samples plated at 40 and 60 C is somewhat unexpected, since the a-Mn type phase transforms to the equilibrium BCC solid solution, which would be expected to increase Bs. The effects may be more of a measurement issue, as many of the annealed samples cracked and delaminated making deposit volume determination, which is necessary to calculate Bs, highly questionable. As such, only Bs values for unannealed samples can be accepted with any certainty. Coercivities (Hc) for as-deposited and annealed CoFe lms are shown in Fig. 14. For as-deposited lms, higher plating temperatures produced deposits with higher coercivities. The deposit plated at 20 C had an average coercivity of 6 Oe, while deposits plated at 40 and 60 C had average coercivities of 27 and 34 Oe, respectively. Coercivity differences are likely related to the identity of the phases and not grain sizes, as the grain size (*10 nm) did not vary much with deposition temperature. The deposit plated at 20 C was entirely single phase (BCC solid solution), and the deposit plated at 60 C was also single phase (a-Mn type phase). The deposit plated at 40 C consisted of a mixture of the two phases. It seems reasonable then that the BCC phase has a much lower coercivity than the a-Mn type phase. This conclusion is borne out in the annealing results. Annealing of the deposits at 174 C led to a signicant reduction in the coercivities of the higher temperature deposits (40 and 60 C), but only a slight reduction in the coercivities of deposits plated at 20 C. The decrease in coercivity for the 40 and 60 C samples is likely due to the partial transformation of the a-Mn type phase to the BCC solid solution. After 4 h of annealing, XRD results indicated that the deposits plated at 40 C (Fig. 10) were almost completely composed of the BCC solid solution phase. As a consequence, the coercivities of these deposits dropped to a level similar to the original coercivities of deposits plated at 20 C. The coercivities of deposits plated at 60 C also dropped when annealed at 174 C; however, since the transformation to the BCC solid solution phase was not complete under these conditions, the coercivities did not drop to the same level as deposits plated at 40 C. In addition, there is a great deal of variation in the coercivities of deposits plated at 60 C and annealed at 174 C, as shown by the two widely spaced

Fig. 11 XRD patterns for CoFe deposits plated at 60 C using standard plating conditions, which were subsequently annealed: a as deposited; b annealed at 174 C; c annealed at 225 C; d annealed at 390 C

for the newly formed BCC solid solution phase. The (330) and (110) crystallographic planes, in the a-Mn type phase and the BCC solid solution, respectively, have similar d-spacings (0.2053 and 0.2006 nm), since the BCC solid solution phase has a lattice parameter that is *1/3 the value for the a-Mn type phase. As such, the transformation of the a-Mn type phase to the BCC solid solution phase appears to involve only slight movement of the Co and Fe atoms. This would account for the conservation of texture during transformation and is consistent with the low transformation temperature (174C), which is prohibitive to the large-scale diffusion of atoms. This texturing effect was also conrmed by TEM analysis [16] and is shown in Fig. 12. Parallel bands aligned perpendicular to the surface are visible in the bright eld (BF) image in Fig. 12a. An SAD pattern (Fig. 12c) from the region shown in Fig. 12a consists of several concentric rings. The more intense rings can be indexed to the BCC solid solution phase, showing that the a-Mn type phase has completely transformed, which conrms the XRD results. There are additional faint rings which are addressed in the next paragraph. The rings belonging to the BCC phase are not continuous, which is evidence of texture. A dark eld (DF) image using part of the (110) reection for the BCC phase is shown in Fig. 12c. The bands are not single grains, but consist of small grains (*20 nm in size) with similar orientations. In fact, neighboring columns also are similarly oriented. These results conrm the XRD results in Fig. 11. The faint rings in Fig. 12c can be indexed to Fe3O4 (magnetite). The oxide was not detected by XRD analysis, but this is likely a consequence of its low concentration. Fe3O4 was also detected in as-deposited samples, so was likely incorporated during electrodeposition. Individual oxide grains were not distinguishable, since the oxide diffraction rings were in close proximity to the rings for the BCC phase. As such, a DF image could not be formed from an oxide ring without contribution from the CoFe phase.

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J Mater Sci: Mater Electron (2011) 22:614625 Fig. 12 TEM micrographs and electron diffraction pattern from the cross-section of a deposit plated at 60 C and annealed at 390 C: a BF image; b DF image; c SAD pattern from deposit. The DF image was taken using the circled portion of ring

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Fig. 13 Saturation magnetic ux densities for CoFe deposits plated at various temperatures, using the standard plating solution and parameters, after annealing at various temperatures. The error bars represent the standard error of the measurements

data points (Fig. 14). The large difference can be attributed to the fact that 174 C represents the temperature for the onset of transformation, so that the amount transformed in a given sample can vary greatly. Samples which have undergone minor amounts of transformation are expected

to exhibit little or no coercivity changes, while those that have undergone signicant transformation will exhibit large coercivity changes. A small decrease in coercivity was observed in deposits plated at 20 C upon annealing at 174 C. Since there was no phase transformation in these deposits, the decrease may be attributed to the self magnetic annealing effect which occurs in ferromagnetic materials even in the absence of an external magnetic eld [37]. The effect is caused by directional ordering of atoms at elevated temperatures due to the presence of internal magnetic elds in the material. Annealing at 245 C increased the coercivities of all the deposits to values between 15 and 20 Oe, while there was no signicant change in coercivity values when the annealing temperature was increased further to 390 C. The similarity in coercivity values shown by all deposits regardless of plating temperature shows that the coercivities of the deposits are primarily related to phase identity. Deposits annealed for 4 h at 245 C and above are completely composed of the BCC solid solution phase. The uniform increase in coercivity of the deposits when annealed above 174 C is likely due to coarsening of the grain structure, which was corroborated by XRD (peak

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phase, resulted in a decrease in coercivities to values approaching those for the deposits plated at 20 C. The decrease in coercivity is attributed to the transformation of the a-Mn type phase to the equilibrium BCC phase during annealing.
Acknowledgments The authors would like to thank the Natural Sciences and Engineering Research Council (NSERC) of Canada and Micralyne Inc. for providing research funding and for providing metallized wafers (Micralyne). The Alberta Centre for Surface Engineering and Science (ACSES) is also acknowledged for providing the XPS analysis.

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4 Summary Phase formation, and the effects on magnetic properties, in CoFe alloys lms electrodeposited from solutions containing sulfate salts of the metals were studied using primarily X-ray diffraction (XRD). The phase structure of electrodeposited alloys was greatly inuenced by the solution pH, plating temperature and the presence of a stabilizing agent (dibasic ammonium citrate). The presence of ammonium citrate promoted the deposition of the equilibrium BCC solid solution phase. In the absence of ammonium citrate, the metastable a-Mn type phase was deposited at 20 C and metastable HCP phases were deposited at higher temperatures (C40 C). Elevated plating temperatures promoted the deposition of metastable phases. In citrate-containing solutions, the BCC phase was plated at 20 C, while only the a-Mn type phase was plated at 60 C. Lowering the solution pH to 2.3 prevented the deposition of metastable phases at all temperatures for solutions with and without ammonium citrate. Deposits plated at 20 C, and consisting of only the equilibrium BCC phase, had the highest magnetic saturation ux densities (2.2 T) and lowest coercivities (6 Oe). Deposits plated at higher temperatures (C40 C), with mixed phases (BCC and metastable a-Mn type phase) or only the a-Mn type phase, had lower magnetic ux densities (B1.9 T) and higher coercivities (C27 Oe). Annealing of mixed phase deposits, and those with only the a-Mn type

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