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Electrochemical and Solid-State Letters, 7 10 C121-C124 2004

C121

1099-0062/2004/7 10 /C121/4/$7.00 © The Electrochemical Society, Inc.

Electrochemical and Solid-State Letters , 7 10 C121-C124 2004 C121 1099-0062/2004/7 10 /C121/4/$7.00 © The Electrochemical

Compositional Control in Electrodeposition of FePt Films

J. J. Mallett, a,z E. B. Svedberg, a,b S. Sayan, a,c A. J. Shapiro, a L. Wielunski, c T. E. Madey, c W. F. Egelhoff, Jr., a and T. P. Moffat a, *

a National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA b Seagate Technology, Pittsburgh, Pennsylvania 15222, USA c Rutgers, The State University, Piscataway, New Jersey 08854, USA

Fe-Pt thin-film alloys have been grown by electrodeposition at potentials positive to that required to deposit elemental Fe. X-ray diffraction studies indicate the formation of fine grained face centered cubic alloys, while Rutherford backscattering spectrscopy and energy-dispersive X-ray spectroscopy reveal substantial incorporation of oxygen in the FePt deposits. The Fe-Pt codeposition process is driven by the negative enthalpy associated with alloy formation. The experimentally determined relationship between alloy composition and the iron group underpotential was found to be in reasonable agreement with free energy calculations for the binary alloy system, based on thermochemical data. © 2004 The Electrochemical Society. DOI: 10.1149/1.1792251 All rights reserved.

Manuscript submitted January 7, 2004; revised manuscript received March 4, 2004. Available electronically September 15, 2004.

There is currently considerable interest in FePt as a high-density perpendicular recording medium, due to the high magnetocrystalline

anisotropy of the L1 0 phase. The significant challenges of achieving

an appropriately oriented L1 0 phase, while maintaining the required grain or particle size of less than 5 nm, remain unsolved, despite considerable effort. 1-3 FePt has attracted additional interest due to its shape-memory properties, and Invar effects, both of potential utility in microelectromechanical systems MEMS . 4 In addition to these useful physical properties Fe-Pt and related alloys have potential application as CO-tolerant electrocatalyst in polymer electrolyte fuel

cells.

5,6

In all the above applications, process control during synthe-

sis is of central importance. A variety of means have been used to produce Fe-Pt and similar alloys ranging from vacuum methods like MBE and sputtering 2,3,7,8

to electrodepositon

9-13

of thin films or fine particle production by

solution phase chemical reduction. 1,14-16 One particular advantage of

electrochemical methods is the ability to easily specify and control the supersaturation while monitoring its effect on growth kinetics. Herein we examine the factors affecting alloy composition dur- ing electrodeposition from an aqueous electrolyte containing chloro- complexes of platinum and iron. Traditional alloy deposition studies

largely focus on growth in the overpotential domain.

17

In this case,

the composition is controlled by the relative rate of reduction of the constituents occurring in a potential regime where both species can be deposited in their elemental form. The desired differential activ- ity, required for a particular alloy composition, is achieved by judi- cious choice of component concentrations and complex forming ligands. In contrast, in this study the use of the free energy of alloy formation to control alloy composition is demonstrated. The thermodynamic basis for alloy formation is well established. In fact, high temperature electrochemical potential emf measure- ments have contributed significantly toward the understanding of phase equilibria and the construction of phase diagrams. A necessary

condition for binary alloy A 1 x B x formation is equality of the elec- trochemical potential of the respective constituents

E A A E B B

1

where E i is the Nernst potential given by

E i E i o

ion

RT

a

i

zF

alloy

a i

ln

2

The free energy of alloy formation is reflected in the activity of the

denominator while i represents the kinetic overpotential or degree of supersaturation. Inspection reveals that alloying i.e., an activity

* Electrochemical Society Active Member. z E-mail: jon.mallett@nist.gov

less than 1 results in a positive shift of the reversible potential for each constituent away from that characteristic of the elemental state. This is equivalent to the formal description of the underpotential

deposition upd phenomenon. 18

Historically, this term has been

used to describe the deposition of submonolayer quantities of a metal onto a foreign substrate wherein the activity was less than

unity. More generally, it is recognized that deviations from a simple linear activity-composition relationship can arise from a combina- tion of effects ranging from alloying interactions to composition driven changes in the surface energy and associated double layer effects. Several early studies of upd systems revealed the occurrence of alloy formation by interdiffusion of the upd overlayer and sub-

strate see, for example, Ref. 18-20 . The subject of Fe group upd on

Pt and other metals has received very limited study;

21

the most

recent being a report of upd of Fe, Co, and Ni on Pt and Au in a nonaqueous electrolyte, although no significant evidence of inter- mixing or alloying was observed.

22

In contrast to traditional upd studies, the role of upd in the direct formation of thin film alloys by codeposition has received less at- tention. Two prototypical cases where the composition of the solid has been correlated with the free energy of phase formation are

CdTe compound formation 23,24 and NiAl alloy deposition. 25 This

approach has also been used to produce Cu-Cd, 26 Cu-Sn,

Cu-Pt, 29 Cu-Pd, 29 and ZnFe, 30

27

Cu-Au, 28

as well as a variety of aluminum 31

alloys. This approach is clearly distinct from traditional alloy depo- sition studies that focus on growth in the overpotential domain. The quantitative connection between underpotential alloy depo- sition and thermochemical data is given by the combination of Eq. 2 and

  • i M

a i alloy i X i exp RT G

3

where the activity coefficient, i , reflects deviations from ideality of

the partial molar free energy of alloying constituent i , G i M , for the

particular phase. The latter may be evaluated from tabulated integral free energy data or related constitutive equations that are available for a wide range of alloys. In the Fe-Pt system, high-temperature measurements of the equi-

libria between Fe-Pt alloys, Fe-oxides, and oxygen 1473-1673 K reveal that fcc Fe-Pt solid solutions exhibit strong negative devia- tions from ideality that may be described by an asymmetric regular solution model

RT ln Fe alloy W G 1 2 W G 2 W G 1 x Fe 1 x Fe 2 4

where the temperature and composition-independent constants are

W G 1 138.0 3.3 kJ/mol and W G 2

90.8 24.0 kJ/mol. 32

C122

Electrochemical and Solid-State Letters, 7 10 C121-C124 2004

C122 Electrochemical and Solid-State Letters , 7 10 C121-C124 2004 Figure 1. The separated cell designed

Figure 1. The separated cell designed to maintain a low activity of Fe 3 and O 2 in the working compartment.

In the present work this result is extrapolated to 298 K for compari- son to the experimentally determined potential dependence of alloy formation. Ordering is an important aspect for systems with strong A-B interactions. Calorimetric measurements for FePt reveal the face-

centered cubic fcc to L1 o transformation, involves an enthalpy of

10.2 2.1 kJ/mol, although this only proceeds at higher tempera-

tures, e.g., 673 K for heating rates of 20 K/min.

33

Kinetic limitations

on the development of long range order during low temperature synthesis results in fcc solid solutions rather than the lower energy ordered phases. 3,7-16 This effect is one of the key obstacles to the

production of ordered L1 o Fe-Pt thin films as media for magnetic storage.

Experimental

Fe-Pt alloys were electrodeposited from an aqueous electrolyte

consisting of 0.11 mol/L FeCl 2

99% , 0.3-30 mmol/L PtCl 4

99.99% and 0.5 mol/L NaCl 99% min . The solutions were made

using 18 M water and adjusted to pH 2.5 ( 3.2 mmol/L H 3 O ). by the addition of hydrochloric acid. The electrolyte was stable against spontaneous Pt decomposition as no visible colloids formed during the experiments. However, to establish a stable environment for the deposition of iron, specific measures were taken to avoid or

minimize the production of Fe 3 . A membrane separated cell,

shown in Fig. 1, enabled the use of a Fe 2 -free NaCl anolyte

( 0.4 L) while a Pt auxiliary electrode in the cathode compartment

( 0.4 L) was used to reduce dissolved O 2 along with any Fe 3 . A saturated calomel reference electrode SCE was held at a fixed position relative to the working electrode and all quoted potentials refer to this scale. A bipotentiostat was used to independently con- trol the working electrode and auxiliary Pt grid electrode.

In a typical experiment the FeCl 2 -NaCl catholyte was pre-

electrolyzed at 0.4 V for an extended period prior to the addition

of PtCl 4 . The electrolyte was first de-aerated by bubbling N 2 for 30 min, followed by blanketing the head space of the cell with flowing

N 2 for the duration of the experiment. After 2 min of pre-electrolysis a cathodic current of 10 mA was measured at the auxiliary Pt elec- trode that diminished to 20 A after 10 h, indicating a decrease of

the combined Fe 3 and O 2 of almost three orders of magnitude.

The PtCl 4 salt was then added to the cell and, simultaneously, the Pt auxiliary grid potential was increased to 0 V in an attempt to mini- mize the loss of platinum due to plating on the grid. The loss was estimated to be under 2.5 mg/h, compared to the 300 mg 3 mmol/L initially added to the cell. This was balanced by the equivalent ad-

dition of PtCl 4 to the cell every 2 h. FePt films were deposited by immersing substrates into the cell with the potential applied. After a fixed period of time the specimens

C122 Electrochemical and Solid-State Letters , 7 10 C121-C124 2004 Figure 1. The separated cell designed

Figure 2. CVs collected at 10 mV/s in a 0.5 mol/L NaCl containing b 3 mmol/L PtCl 4 , c 0.11 mol/L FeCl 2 , and d 3 mmol/L PtCl 4 and 0.11 mol/L FeCl 2 .

were quickly removed and rinsed before disconnecting from the potentiostat. Deposition was performed at room temperature

( 294 K) under quiescent conditions. Substrates were prepared by

electron-beam evaporation of 100 nm of copper, or silver, onto

Si 100 wafers which either had a 9 nm Ti adhesion layer or for

purposes of

texturing had been H-terminated

with

a

10%

HF

solution.

Results and Discussion

Cyclic voltammetry CV was used to investigate the deposition process on mechanically polished Pt plate working electrodes. Fig- ure 2a shows the voltammetric response of a Pt electrode in de-

aerated 0.5 mol/L NaCl. The current rise at 0.2 V is due to proton

reduction ( E H /H2 0.213 V for a H2 10 6 ) that is diffusion

limited below 0.45 V. This is followed by water reduction at

0.8 V. On the positive going sweep the reverse reactions are

evident, with H 2 oxidation occurring at 0.5 V. The shift in the

H /H 2 potential toward more negative values is due to a change in

the interfacial pH ( 4.4) associated with proton depletion com-

bined with enrichment of H 2 near the interface i.e., gas bubbles

attached to the electrode . The addition of 3 mmol/L PtCl 4 results in the onset of platinum deposition below 0.3 V. As shown in Fig. 2b the reaction is independent of potential below 0.0 V, most likely due

Electrochemical and Solid-State Letters, 7 10 C121-C124 2004 C123

to transport limitation. Likewise, proton reduction is transport lim-

ited beyond 0.35 V; a slightly more positive value than that ob- served in the absence of Pt deposition reflecting the enhanced cata- lytic nature of freshly deposited platinum. Interestingly, bright specular Pt films, greater than 1 m in thickness, were obtained by

potentiostatic growth between 0.0 and 0.7 V from an electrolyte

containing 30 mmol/L PtCl 4 . This observation is surprising in light of the Mullins-Sekerka instability that is usually associated with transport limited deposition reactions. 34 Deposition at more negative potentials results in rough black deposits.

Voltammetry in the FeCl 2 -NaCl electrolyte Fig. 2c reveals the

onset of diffusion limited proton reduction at 0.45 followed by

iron deposition and water reduction below 0.8 V. During the re-

verse sweep iron dissolution occurs between 0.75 and 0.4 V and involves at least two processes as reflected by the two peaks in the

stripping wave. At positive potentials beyond 0.3 V oxidation of

Fe 2 to Fe 3 is evident.

To obtain an estimate of the reversible Fe/Fe 2 potential the voltammetric behavior of an iron wire electrode not shown was

examined. The open-circuit potential OCP was 0.72 V, that is

close to the zero-current potential, 0.75 V observed in Fig. 2c. This mixed potential is associated with the balance between iron dissolution and proton reduction. Small potential voltammetric ex- cursions of the iron wire about the OCP indicate that the reversible

potential for the Fe/Fe 2 reaction is close to 0.75 V. Figure 2d shows the voltammetric behavior for the complete Fe-Pt plating electrolyte. At potentials below 0 V the current ex- ceeds that associated with platinum deposition and proton reduction. The disparity increases with decreasing potential and is attributed to iron codeposition with platinum. A small peak is observed at

0.53 V followed by a marked increase in the deposition rate at

potentials below 0.7 V. On the reverse sweep the onset of iron

dissolution is evident at 0.68 V although the stripping wave is

displaced to more positive potentials, 0.5 V, compared to pure

iron. Inhibition of iron dissolution is due to ( i ) stabilization pro- vided by alloy formation combined with the kinetic resistance asso- ciated with dissolution through the platinum enriched overlayer that

develops with dealloying and/or ( ii ) continued platinum deposition that occurs during the positive-going sweep. Knowledge of the cur- rent efficiency of the partial deposition reactions is required to cal- culate the alloy composition from these measurements. Alloy formation was unambiguously demonstrated by growing a series of FePt films by potentiostatic deposition over a range of potentials followed by compositional and structural analysis. Films

deposited between 0.2 and 0.7 V were specular even for thick- nesses of several micrometers corresponding to several hours of deposition. In contrast, films deposited at more negative potential,

i.e., 0.8 V, were black due to high surface roughness. This is similar to the results described earlier for the deposition of elemental platinum. The compositions of the thin films were measured by energy dispersive X-ray spectroscopy EDS and Rutherford backscattering

spectrometry RBS . An 2 MeV He 2 RBS spectrum for a FePt film

deposited on a Cu poly /Ti/Si 100 substrate at 0.7 V is shown in Fig. 3. A substantial quantity of oxygen was incorporated in the films. The oxygen levels appear to scale with the iron concentration in the deposit. The quantitative fit indicates the film is 107 nm thick with an iron content of 0.53 atomic fraction with respect to Pt al-

though the film contains 0.25 atomic fraction of O with respect to Fe and Pt. The metal composition, i.e., Fe and Pt, determined by EDS and RBS differ by less than 0.10 atomic fraction. This is as- cribed to a systematic error associated with the finite film thickness algorithm used for the quantitative EDS analysis. Structural characterization was performed by symmetric X-ray diffraction XRD . In Fig. 4, a -2 XRD spectrum is shown for a

100 nm thick FePt film grown on a Cu 100 //Si 100 substrate at

0.7 V. The film has an fcc structure and is slightly textured in the

Electrochemical and Solid-State Letters , 7 10 C121-C124 2004 C123 to transport limitation. Likewise, proton reduction

Figure 3. RBS spectrum of a 107 nm thick FePt film deposited at 0.7 V SCE and a four-layer FePt/Cu/Ti/Si model fit.

100 direction as suggested by the FePt 200 shoulder on the Cu 200 substrate peak. The peaks corresponding to FePt 111 and 311 scattering are also evident. A coherence length of 3.5 nm was calculated from the peak widths using the Scherrer formula. This indicates that the film has a very fine grain size. For different films the peak positions shift to higher diffraction angles as the film growth potential was decreased not shown . This reflects the iron content in the films and was quantified by combining lattice param- eter measurements from the 111 peak with Vegard’s linear ap- proximation. For the same samples the coherence length varied be- tween 8.0 and 1.9 nm. No evidence for the formation of crystalline iron oxides was observed despite the high oxygen content in the films. Importantly, annealing the films grown on copper substrates at

0.65 V results in the formation of L1 o phase. A detailed report of the effects of annealing on the structural and magnetic properties will be given elsewhere. The RBS, EDS, and XRD measurements reveal the potential dependence of FePt film composition as summarized in Fig. 5. By

referencing the potential to the estimated Fe/Fe 2 reversible poten-

Figure 4. XRD spectrum of a 700 mV. 100 nm thick FePt film deposited at
Figure 4. XRD spectrum of a
700 mV.
100
nm
thick
FePt
film
deposited
at

C124

Electrochemical and Solid-State Letters, 7 10 C121-C124 2004

C124 Electrochemical and Solid-State Letters , 7 10 C121-C124 2004 Figure 5. The experimentally determined composition

Figure 5. The experimentally determined composition of FePt alloys, ne- glecting the oxygen content, compared to prediction based on thermochemi- cal data Eq. 4 .

tial ( 0.75 V) the top scale shows that codeposition of Fe takes place by underpotential deposition. The solid curve is the result of free energy calculations for the Fe-Pt binary system, based on Eq. 4. The favorable agreement between fcc FePt thermochemical data and the electroplating experiments, despite the presence of oxygen in the film, suggests that thermodynamic factors dominate over kinetics in determining alloy composition. Significant oxygen incorporation has been noted previously for iron and nickel deposition from simple chloride solution at pH of 3.0. 35 The apparent insensitivity to oxy- gen may simply be a fortuitous outcome of an overly simplest com- parison or may reflect minimal perturbation of the interaction be- tween Fe-Pt by interstitial oxygen. We also note for the sake of completeness that the interstitial oxygen content of the alloys used in Ref. 32, i.e., Eq. 4, was not reported. The argument for thermochemically controlled codeposition is further supported by RBS measurements demonstrating insensitivity

of alloy composition to variations in the PtCl 4 concentration. Spe-

cifically, a series of film were grown at 0.6 V while PtCl 4 was varied over two orders of magnitude resulting in variations of the iron content of less than 0.05 atomic fraction of metal. Thus, alloy formation proceeds at a rate determined by the reduction of the platinum complex accompanied by kinetically facile iron codeposition. Related alloy systems, such as Co-Pt and Ni-Pt, exhibit similar negative deviations from ideal solution behavior and are expected to demonstrate similar codeposition behavior. Preliminary experiments provide solid support for this conclusion. A significant limitation on calculating the potential dependence of codeposition is the lack of reliable low-temperature bulk phase thermochemical data. This is further hampered by limited knowledge of interfacial energies, seg- regation effects, etc. Nevertheless, the codeposition process is clearly relevant to determining alloy composition in related pro- cesses such as particle production by chemical reduction. In this case, the electrochemical potential is determined by the strength of the reducing agent and concentration of the reactants as opposed to an external potentiostat. In a related fashion, the strong interactions between iron group metals and Pt or Pd suggests caution in inter- preting prior reports of Fe-Pt, Co-Pt multilayer production from single electrolyte systems. Many of these studies are incorrectly based on the linear combination of elemental behaviors. In contrast

electrochemical atomic layer epitaxy ECALE 36 may offer an inter-

esting alternative for obtaining layer-by-layer growth of ordered L1 0 FePt and related phases.

Conclusions

A series of bright fine grained fcc Fe-Pt thin film alloys have been grown at potentials positive to that required to deposit elemen- tal Fe. The codeposition process is driven by the negative enthalpy associated with alloy formation. The relationship between alloy composition and the iron group underpotential was established ex- perimentally and found to be in reasonable agreement with free energy calculations based on available thermochemical data. The construct is broadly applicable and of particular interest for alloy systems such as Co-Pt, Fe-Pd, and related combinations.

The National Institute of Standards and Technology assisted in meeting the publication costs of this article.

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