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Acta Materialia 56 (2008) 3940–3950

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Atomic mobilities, diffusivities and simulation of diffusion growth

in the Co–Si system
L. Zhang a, Y. Du a,*, Y. Ouyang b, H. Xu a, X.-G. Lu c, Y. Liu d, Y. Kong a, J. Wang a
a
State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, China
b
Department of Physics, Guangxi University, Nanning, Guangxi 530004, China
c
Thermo-Calc Software AB, Stockholm Technology Park, Björnnäsvägen 21 SE-113 47, Stockholm, Sweden
d
Western Transportation Institute, Montana State University, Bozeman, MT 59715, USA

Received 25 March 2008; received in revised form 9 April 2008; accepted 13 April 2008
Available online 22 May 2008

Abstract

Atomic mobilities of both Co and Si in all the solid phases of the Co–Si system were obtained through assessments of experimen-
tally determined diffusion coefficients from the present work and the literature by the DICTRA (diffusion-controlled transformations)
simulation package. The first-principles calculations were performed to clarify the contradictory impurity diffusion coefficients of Co
in Si by determining the diffusion activation energy. The concept of ‘‘average thermodynamic factor” was extended to model binary
compounds with certain homogeneity ranges. Based on the atomic mobilities obtained, the diffusion growths of the compounds in
wide temperature ranges were predicted. Comprehensive comparisons show that most of the experimental data resulting from diffusion
phenomena are well reproduced by the parameters obtained. The approach is of general validity and applicable to establish mobility
databases of technically important alloys.
Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Co–Si system; Atomic mobility; Diffusion growth; First-principles calculations

1. Introduction cesses [4–8], such as diffusion in systems with B2 ordering,

Comprehensive understanding of the bulk diffusion pro-
cess in multicomponent alloys is essential in various appli-
cations, such as solidification, creep, homogenization,
precipitation, re-crystallization and protective coatings
[1,2]. Computer simulation has become an important and
effective tool for gaining insight into complex materials
processes. For the purpose of simulating diffusion-con-
trolled transformations in multicomponent systems, the
DICTRA (diffusion-controlled transformations) software
package [3] has been developed. Based on sharp interface
and local equilibrium hypothesis, DICTRA has been used
successfully to simulate various phase transformation pro-
* binary stoichiometric compounds by introducing the
Corresponding author. Tel.: +86 731 8836213; fax: +86 731 8710855.
E-mail addresses: yong-du@mail.csu.edu.cn, caphld@mail.csu.edu.cn
(Y. Du).
cementite dissolution during austenitization, solidification,
caburization and coarsening of carbides. The quality of
DICTRA simulations is critically dependent on the accu-
racy of both thermodynamic and kinetic data. Reliable
thermodynamic databases for various alloy systems are
available [9]. In contrast, experimentally determined diffu-
sion coefficient data are not generally assessed, and data
from different sources are often not mutually consistent.
Thus, there is an urgent need to remedy this situation.
To the best of the authors’ knowledge, DICTRA soft-
ware has only been used to model the diffusion of phases
showing large homogeneity ranges, such as terminal solid
solutions. Recently, Du and Schuster [10] proposed an
effective approach to describing the diffusion growth of
concept of average thermodynamic factor. It would be of
great interest to extend this approach to model the diffusion

1359-6454/$34.00 Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2008.04.017
 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950
growth of binary intermediate compounds with certain
homogeneity ranges.
The Co–Si system is chosen as the target because of its
technical importance [11] and fundamental scientific inter-
est for diffusion phenomenon. Most recently, the present
authors [12] provided the precise thermodynamic parame-
ters for this system. Thus, the main objectives of the pres-
ent work are (1) to measure the diffusion growth of the Co–
Si binary compounds and the inter-diffusion coefficients of
the (aCo) phase at 1050 °C; (2) to clarify the contradictory
impurity diffusion coefficients of Co in Si via first-principles
calculations; (3) to obtain self-consistent atomic mobility
parameters for both Co and Si in various solid phases of
the Co–Si system via DICTRA simulations; and (4) to
describe the diffusion growth of the compounds in a wide
temperature range.
2. Literature data on diffusion growth and diffusivities of
Co–Si binary phases
2.1. Diffusion growth of Co–Si binary phases
Jan et al. [13], Kim et al. [14] and Barge et al. [15] have
studied the reactive diffusion in the Co–Si system by means
of bulk Co/Si diffusion couples in the temperature range
700–1050 °C. They found that three intermediate phases
(Co2Si, CoSi and CoSi2) grow according to the parabolic
law, implying diffusion-controlled transformation. The
observed thicknesses of the intermediate phases at different
temperatures were reported, and their corresponding
growth rate constants were presented [13–15]. van Dal
et al. [16] investigated the reactive diffusion of the single-
intermediate phase by diffusion couples consisting of the
saturated adjacent phases over the temperature range
914–1217 °C. The width of the intermediate phase was
also observed to grow via a diffusion-controlled mecha-
nism. The thickness of the CoSi phase in bulk Co2Si/CoSi2
diffusion couples was also measured by van Dal et al. [16].
2.2. Diffusion coefficients of Co–Si binary phases
Three kinds of diffusion coefficients in the Co–Si system
are available in the literature, including (a) self-diffusion
coefficients of Co and Si in both pure elements and com-
pounds, (b) impurity diffusion coefficients of Co in Si and
(c) inter-diffusion coefficients in the (aCo) phase. All the data
are summarized in Table 1 and categorized in the following.
Self-diffusion of Co in pure Co has been studied by
many groups [17–26] using various methods. The measure-
ments [17–22,24,25] focused mainly on the very narrow
temperature ranges, using the conventional mechanical sec-
tioning technique, while Bussmann et al. [23] and Lee et al.
[26] studied the self-diffusion in pure Co over wide temper-
ature ranges through a combination of sputter sectioning
and serial lathe sectioning. The results [23,26] are in good
agreement. Consequently, the data from Bussmann et al.
[23] and Lee et al. [26] are used in the present optimization,
3941
while those from the other sources [17–22,24,25] are not
considered.
Many investigators [27–40] focused on the measure-
ments of self-diffusion coefficients of Si in pure Si. Owing
to the short half-life of the radiotracer 31Si (2.6 h), the
reported Si self-diffusion coefficients are limited in a narrow
temperature range [28–30,32,33]. The stable isotope 30Si
used in these studies [27,34–36] has the disadvantage that
the 30Si background concentration in natural Si is high
(3.10%). To overcome the difficulties mentioned above,
Bracht et al. [37] employed highly isotopically enriched
28
Si layers as well as the secondary ion mass spectrometry
(SIMS) technique to measure the self-diffusion coefficient
of Si in pure Si in the temperature range 850–1388 °C.
These data are consistent with those from Ural et al.
[38,39]. Recently, Shimizu et al. [40] measured the self-dif-
fusion coefficients of Si at temperatures 735–875 °C based
on the Raman shift of longitudinal optical phonon fre-
quencies of diffusion annealed 28Si/30Si isotope superlattic-
es. However, the data from Shimizu et al. [40] cannot be
used in the present assessment, as grain boundary diffusion
is enhanced significantly at lower temperatures, and the
DICTRA software employed in the present work can only
treat volume diffusion at higher temperatures [3]. As a
result, only the data from Bracht et al. [37] and Ural
et al. [38,39] are used in the present work, while others
[27–36] are used to verify the reliability of the atomic
mobilities obtained .
In addition to the above self-diffusion in pure elements,
self-diffusion coefficients of Co and Si in various intermedi-
ate compounds have also been investigated by two groups
of authors [16,41]. As shown in Table 1, van Dal et al. [16]
obtained the tracer diffusion coefficients of Co and Si in the
CoSi2 and CoSi phases by employing the concept of inte-
grated diffusion coefficient. The fact that Si is virtually
the only mobile species in the CoSi phase was also reported
by van Dal et al. [16]. These self-diffusion coefficients of Co
and Si in intermediate compounds [16,41] are used in the
present work to evaluate the atomic mobilities of the ele-
ments in the corresponding compounds.
The impurity diffusion of Co in Si was reported by
Bakhadyrkhanov et al. [42], and then reviewed by Weber
[43]. Subsequently, several researches [44–50] measured
the impurity diffusion of Co in Si using different methods.
These reported data [44–50] fall into three categories. As
shown in Fig. 1, large deviations exist among the reported
data. In the present work, first-principles calculations are
performed to determine the diffusion activation energy of
Co in Si following the mono-vacancy diffusion mechanism,
as described later.
As for the inter-diffusion coefficients, only one piece of
experimental information exists in the literature, which is
also listed in Table 1. However, only those values
>1050 °C from Yamamoto et al. [51] are used in the present
assessment, owing to the discrepancy between the inter-dif-
fusion coefficients at 1050 °C in the Co-rich region from
Yamamoto et al. [51] and the present work, as well as the
3942 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950

Table 1
Summary of various diffusion coefficients in the Co–Si system
Type of data Temperature Method Ref. Codea
range (°C)
Self-diffusion In pure Co: 1050–1250 Radioactive 60Co: decrease in surface activity method; purity: 99.06 wt.% Co and [17,18] h
coefficients of Co DCo
Co 99.7 wt.% electrolytic Co
ðDCo Þ 1000–1265 Radioactive 60Co: decrease in surface activity method; purity: >99.9 wt.% Co [19] h
1104–1406 Radioactive 60Co: sectioning and counting; purity: >99.9 wt.% Co [20] h
701–1297 Radiation of 60Co: residual-activity technique [21] h
1015–1300 Radioactive 60Co: sectioning and counting; purity: 99.45 wt.% Co [22] h
623–1472 Standard radio-tracer (57Co and 60Co) thin-layer-sectioning technique; serial [23] j
lathe sectioning (>1127 °C) and sputter sectioning (<1127 °C); purity: 99.99 wt.%
polycrystalline Co
873 Radioactive 60Co: IBSb serial microsectioning; purity: 99.996 wt.% Co [24,25] h
650–1470 The serial radio-frequency (57Co and 60Co) sputter microsectioning method [26] j
(<1445 °C); serial lathe sectioning method (>1445 °C); purity: >99.999 wt.%
single-crystal Co

In CoSi2 914–1217 BDC,b integrated diffusion coefficients [16] j

phase: 760–1100 Radioactive 60Co: conventional sectioning [41] j
DCoSi
Co
2

30
Self-diffusion In pure Si: 1178, 1300 Si radioactivation: chemical sectioning [27] h
coefficients of Si DSi
Si 1200–1400 Radio-isotope 31Si: hand-lapping sectioning [28] h
ðDSi Þ 1000–1300 Radioactive 31Si: electrochemical sectioning [29,30] h
970–1070 Electron microscope observation: loop annealing [31] h
1047–1390 Radiotracer (31Si): sputter sectioning [31] h
900–1000 Radioactvie 30Si: (p, c) resonance broadening method [34] h
885–1175 Isotope 30Si: ion-analyzer technique [35] h
830–1200 Isotope 30Si: ion implantation; p, c-reaction technique [36] h
850–1388 Isotopically enriched 28Si layers: SIMSb technique [37] j
800–1100 Isotopically enriched 30Si layers: SIMSb technique [38,39] j
735–875 Raman spectroscopy [40] +

In B-doped 1000–1250 Radiotracer (31Si): sputter sectioning [33] +

Si: DSi
Si
In CoSi 914–1217 BDCb: integrated diffusion coefficients [16] j
phase:
DCoSi
Si
In CoSi2 914–1217 BDCb: integrated diffusion coefficients [16] j
phase:
DCoSi
Si
2

Impurity diffusion coefficients of Co 1000–1300 Radioactive isotope 56Co: successive removal of layers [42] +
in Si ðDSi
Co Þ 900–1200 Radioactive 57Co: successive removing and counting [44] j
1125–1225 Electrically active Co: spreading resistance technique [45] j
1000–1200 Electrically active Co: DLTSb; ICTSb [46] j
1100 Electrically active Co: DLTSb [47] j
1050–1150 Radioactive 60Co: SIMSb [48] +
700–1000 Electrically active Co: DLTSb [49] j
760–1100 Radioactive 57Co: sectioning technique [50] +

Inter-diffusion coefficients in (aCo) 1000–1200 BDCb (vapor–solid), BMMb, EPMAb [51] M

e
phase ð DÞ 1050 BDCb (solid–solid), BMMb, EPMAb TW h
a
Indicates whether the data are used or not used in the atomic mobility assessment: j, used; M, partly used; h, not used but considered as reliable data
for checking the parameters; +, not used.
b
BDC = bulk diffusion couple; BMM = Boltzmann–Matano method; DLTS = deep level transient spectrometry; EPMA = electron probe micro-
analysis; IBS = ion-beam sputtering; ICTS = isothermal capacitance transient spectrometry; SIMS = secondary ion mass spectrometry; TW = this work.

overlap of those inter-diffusion coefficients at 1000 and
1050 °C [51].
3. Experimental procedure
Co pieces (purity 99.95 wt.%) and Si pieces (purity
99.99 wt.%) were used as the starting materials. First, one
Co–10 at.% Si alloy was prepared in an arc melting furnace
(WKDHL-I, Opto-electronics Co. Ltd., Beijing, China)
under a high purity argon atmosphere using a non-consum-
able W electrode. The button was re-melted five times to
improve its homogeneity. No chemical analysis for the
alloy was conducted, as the weight loss during arc-melting
was <0.5 wt.%.
 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950 3943

Andersson and Ågren [52] and later modified by Jönsson

[53], Mi is expressed as
   
RT ln M 0i Qi 1 mg
M i ¼ exp exp  C ð1Þ
RT RT RT
where R is the gas constant, and T is the temperature. mgC
is a factor taking into account the ferromagnetic contribu-
tion to the diffusion coefficient. For non-bcc phases, the
ferromagnetic effect on diffusion is negligible [54]. Conse-
quently, it is sufficient to combine Qi and RT ln M 0i into
one parameter DGi ¼ Qi þ RT ln M 0i .
For the solid solution phase U (U = (aCo) or (eCo) or
(Si)) in the Co–Si system, DG/i is described by the following
expression:
DGUi ¼ xCo DGCo Si 0 Co;Si
i þ xSi DGi þ xCo xSi D Gi
Fig. 1. The conflicting experimental impurity diffusion coefficients of Co
þ xCo xSi ðxCo  xSi ÞD1 GCo;Si
i þ  ði ¼ Co or SiÞ
in Si in the literature from different sources [42,44–50]. The reported
impurity diffusion coefficients of Co in Si in Refs. [44–47,49] are adopted ð2Þ
in the present work, considering the good agreement between the
experimental diffusion activation energy (269,767 J mol1) from Refs. in which DGCoi and DGSi U
i are the values of DGi for pure Co
[44–47,49] and the calculated one (243,151 J mol1) by the present first- and Si, respectively, and thus represent the endpoint values
principles simulations. The error bars for experimental data are shown in in the composition space. Dj GCo;Si
i ðj ¼ 0; 1; . . .Þ are the bin-
the diagram in the cases they are reported in the literature.
ary interaction parameters between Co and Si.
Assuming the mono-vacancy mechanism for diffusion
Then, five Co pieces and four Si pieces, as well as one Co– and neglecting correlation factors [52,53], the tracer diffu-
10 at.% Si alloy, were cut into bars with approximate dimen- sivity Di is related to the mobility Mi by the Einstein
sion of 5  4  12 mm3. After grounding and polishing, four relation:
Co pieces and four Si pieces were bound together with Mo Di ¼ RTM i ð3Þ
wires to make four Co/Si diffusion couples, while the remain-
ing Co piece and the Co–10 at.% Si alloy made one Co/Co–
10 at.% Si diffusion couple. The diffusion assemblies were 4.2. Diffusivities in intermediate compounds
then sealed in an evacuated silica capsule under vacuum
(1 Pa). The four Co/Si diffusion couples were subjected to In order to describe the diffusion behavior of the binary
annealing at 1050 ± 1 °C for 12, 48, 96 and 192 h, respec- compounds with negligible homogeneities, Du and Schus-
tively, while the Co/Co–10 at.% Si diffusion couple at ter [10] introduced the concept of ‘‘average thermodynamic
1050 ± 1 °C for 192 h, followed by water quenching. After factor”, and successfully described the diffusion growths of
standard metallographic preparation, the microstructure the compounds in the Ni–Si system. The present work
observation and phase identification of Co/Si diffusion cou- extends the concept of ‘‘average thermodynamic factor”
ples were performed via optical microscopy (Leica DMLP, to the compounds (aCo2Si and CoSi) with noticeable
Wetzlar, Germany) and scanning electron microscopy with homogeneities in the Co–Si system. As for the stoichiome-
energy dispersive X-ray (SEM/EDX) analysis (JSM- tric CoSi2 compound, a very narrow homogeneity range is
5600LV, JEOL, Japan). The thicknesses for the observed introduced by slightly modifying the thermodynamic
phases in each Co/Si diffusion couple were thereafter deter- parameters for this phase, as reported in [12]. Assuming
mined. As for the Co/Co–10 at.% Si diffusion couple, the no volume change, the inter-diffusion coefficient of the
CoSi phase ð D e CoSi Þ with certain homogeneity range is
determination of phase composition was performed via elec-
tron probe microanalysis (EPMA) (JXA-8800R, JEOL, related to tracer self-diffusion coefficients (DCo Si
CoSi and DCoSi Þ:
Japan) to obtain the Si concentration–penetration profile. e CoSi ¼ ðDCo  xSi þ DSi  xCo Þ  /
D CoSi CoSi ð4Þ
4. Modeling where / and xi (i = Co or Si) are the thermodynamic factor
and mole fraction of species i, respectively. The term / can
4.1. Atomic mobility of elements in solid solutions be given by
o ln cCo o ln cSi
Based on absolute reaction rate theory, the atomic /¼1þ ¼1þ ð5Þ
mobility for an element i, Mi, may be divided into a fre- o ln xCo o ln xSi
quency factor M 0i and an activation enthalpy Qi. Both M 0i in which ci (i = Co or Si) is the activity coefficient of species
and Qi are, in general, dependent on composition, temper- i in the CoSi phase. As shown in Fig. 2, / for the CoSi
ature and pressure. According to the model suggested by phase changes significantly around its stoichiometric
3944 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950
Fig. 2. Thermodynamic factor of CoSi phase at 1050 °C. x0CoSi and x1CoSi
are the homogeneity limits calculated according to the thermodynamic
parameters from Zhang et al. [12].
composition. In fact, for a strict stoichiometric compound,
/ is infinite. To circumvent this problem, an average ther-
modynamic factor /ave is proposed for the CoSi phase:
Z x1
1 CoSi
/ave ¼ ðx1CoSi  x0CoSi Þ  /  dx ð6Þ
x0CoSi
where x0CoSi and x1CoSi are the homogeneity limits of the CoSi
phase and can be calculated directly from the thermody-
namic parameters. The integral in Eq. (6) is dominated
by the value of / at the stoichiometric composition.
Replacing / in Eq. (4) by /ave, one can get the average in-
ter-diffusion coefficient of the CoSi phase:
e ave ¼ ðDCo  xSi þ DSi  xCo Þ  /ave
D CoSi CoSi CoSi
Equations similar to Eqs. (5)–(7) can be derived for the
aCo2Si and CoSi2 phases. With the known average inter-
diffusion coefficients, Fick’s first and second laws can be
solved numerically for the aCo2Si, CoSi and CoSi2 phases.
4.3. Calculation of activation energy for Co diffusion in Si
The first-principles calculations were performed using
the scalar relativistic all-electron Blöchl’s projector aug-
mented wave (PAW) approach [55,56] within the general-
ized gradient approximation (GGA), as implemented in
the highly efficient Vienna ab initio simulation package
(VASP) [57,58]. For the GGA exchange-correlation func-
tion, the Perdew–Wang parameterization (PW91) [59,60]
was employed. A plane-wave energy cutoff of 400 eV was
employed. The 2  2  2 supercell includes 62 silicon
atoms, one cobalt atom and one vacancy, with Co and
the vacancy being the nearest neighbors. The k-point
meshes for Brillouin zone sampling were constructed using
the Monkhorst–Pack scheme [61] in the present calcula-
tion. The total energy differences were converged to within
10 meV atom1. For the solute diffusion in the diamond
lattice, the exchange of a solute atom with the adjacent
vacancy along the h1 1 1i direction was considered. Diffu-
sion energy barriers for solutes were calculated by displac-
ing the solutes in the h1 1 1i direction: for each fixed solute
atom position, the host atom position was fully relaxed, the
migration energy was obtained as the total energy differ-
ences between the solute atom at the saddle point and at
the initial lattice site, as shown in Fig. 3. The vacancy for-
mation energy, which is adjacent to the solute atom, is the
sum of the vacancy formation energy in elemental silicon
and the solute–vacancy binding energy. The diffusion acti-
vation energy is the sum of the vacancy formation energy
and the solute migration barrier.
5. Results and discussion
5.1. Experimental aspect
Fig. 4 shows a typical backscatter electron image (BEI)
of the Co/Si diffusion couple, which was annealed at
1050 °C for 192 h. Obviously, all the equilibrated phases,
i.e., (aCo), (eCo), Co2Si, CoSi, CoSi2 and (Si) are formed.
This is consistent with the Co–Si phase diagram assessed by
Ishida et al. [62] and calculated by Zhang et al. [12]. As
shown in Fig. 4, the CoSi layer is the thickest, followed
by the Co2Si layer, and the CoSi2 layer is the thinnest
among the three intermediate silicide layers.
In Fig. 5a, the square of the thicknesses of the two
phases Co2Si and CoSi varies linearly with the annealing
time, indicating that the growth of the two phases follows
the parabolic law. The thickness of the CoSi2 phase is too
small to determine accurately using SEM. The parabolic
growth constants of Co2Si and CoSi phases, plotted as a
function of 1000/T, are shown in Fig. 5b and c, respec-
ð7Þ
tively. The solid lines shown in the above two figures were
obtained according to the present work and the literature
[13–15,63]. The growth constants of Co2Si and CoSi phases
obtained by Lau et al. [63] using thick thin-film Co/Si dif-
fusion couples (200 nm of Co on bulk Si) are also shown
in Fig. 5b and c, respectively. As shown in Fig. 5b and c,
Fig. 3. Definition of the migration energy barrier for solute migration
along the h1 1 1i direction in the diamond lattice. The filled circles, unfilled
circles and squares are solute atoms, solvent atoms and vacancies,
respectively.
 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950 3945

the present data are in good agreement with the other

experimental values [13–15,63] within the estimated errors.
The concentration–penetration profile over the entire
diffusion zone in the Co/Co–10 at.% Si diffusion couple
determined by EPMA is shown in Fig. 6a. The profile
was analyzed using the Boltzmann–Matano method [64]
to obtain the inter-diffusion coefficients. Fig. 6b shows
the measured composition dependence of the inter-diffu-
sion coefficients for the Co/Co–10 at.% Si couple at
1050 °C in the (aCo) phase.

5.2. Modeling aspect

The vacancy-mediated solute diffusion in a close-packed

diamond lattice can be analyzed by employing the transi-
Fig. 4. Backscatter electron image (BEI) of the Co/Si diffusion couples tion state theory. The mono-vacancy diffusion mechanism
annealed at 1050 °C for 192 h in the present work. is the simplest among several diffusion mechanisms and

Fig. 5. (a) The relationship between the square of the thickness for Co2Si and CoSi phases and the diffusion time at 1050 °C; Arrhenius plot for the
parabolic growth constants of (b) the Co2Si phase and (c) the CoSi phase in the Co/Si diffusion couples from the literature [13–15,63] and the present work.
The light solid lines denote the maximal errors. The error bars for experimental data are shown in the diagrams in the cases they are reported in the
literature.
3946 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950

Fig. 6. (a) Concentration profile for the Co/Co–10 at.% Si couple annealed at 1050 °C for 192 h; (b) composition dependence of the inter-diffusion
coefficients for the Co/Co–10 at.% Si couple at 1050 °C for 192 h.

can be modeled effectively. The calculated formation
energy of the vacancy adjacent to the solute atom is
2.58 eV. The present calculation indicates that the migra-
tion barrier of the solute is very small in magnitude, with
a value of 0.06 eV. Such a small migration barrier means
that there is almost no energy barrier for the diffusion of
Co from the lattice site to the site of vacancy. This is due
to the positive solution energy of Co in Si. The calculated
solution energy for Co in Si is 0.024 eV atom1. The pres-
ent calculated diffusion activation energy of Co in Si fol-
lowing the mono-vacancy diffusion mechanism is thus
2.52 eV, i.e., 243,151 J mol1, according to density func-
tional theory (DFT). This first-principles calculated value
is in good agreement with the assessed value of
269,767 J mol1, which is based on the experimental data
[44–47,49]. The calculated result deviates substantially
from the experimental values of 144,518 J mol1 [48] and
35,648 J mol1 [50]. Consequently, the experimental impu-
rity diffusion coefficients of Co in Si reported in Refs. [44–
47,49] are regarded as reasonable in the present work.
In order to perform kinetic assessments for the solid
phases ((aCo), (eCo), aCo2Si, CoSi, CoSi2, (Si) phases) in
the Co–Si system, slight modifications to the previous ther-
modynamic modeling [12] should be made in order to
introduce small homogeneity ranges for CoSi2 and (Si)
phases. Table 2 lists the newly evaluated thermodynamic
parameters for the two phases. The thermodynamic param-
eters for the other phases are the same as those in Ref. [12].
The assessment of atomic mobilities for the Co–Si sys-
tem is conducted in two steps. In the first step, the atomic
mobilities of Co and Si in solution phases, i.e., (aCo), (eCo)
and (Si), are evaluated using the PARROT module [65] in
the DICTRA software package, based on all the critically
reviewed experiment data from the literature and the pres-
ent work. For the (aCo) phase, it is unnecessary to assess
all the parameters in Eq. (2), considering the limited exper-
imental data in this phase. Here, the frequency factors of
DGSi Si
Co and DGSi are assumed to be 0.5 times and 10 times
that of the self-diffusivity of Fe [66], while their activation
enthalpies equal the self-diffusivity of Fe [66]. The other
parameters ðDGCo Co 0 Co;Si
Co ; DGSi , D GCo and D0 GCo;Si
Si Þ are opti-
mized based on the experimental diffusivities. Owing to
the lack of experimental information, the atomic mobility
for (eCo) phase is assumed to be identical to that of
(aCo) phase. For the (Si) phase, DGSi Si can be optimized
from those assessed experimental self-diffusion coefficients
of Si in pure Si, and DGSi Co was extracted from the experi-
mental impurity diffusion coefficients of Co in Si by [44–
47,49]. As described above, the present first-principles cal-
culation indicates that these experimental data [44–47,49]
are reliable. As the solubility of Co in (Si) is nearly negligi-
ble, it is reasonable to assume that DGSi Si
Co and DGSi are

Table 2
Summary of the adopted thermodynamic parameters of CoSi2 and (Si) phases in the Co–Si systema
CoSi2: (Co,Si)1/3(Co,Si)2/3
0
GCoSi 1 SER 2 SER
Co:Si  3  H Co  3  H Si
2
¼ 41239:2 þ 116:62481  T  20:17772  T  ln T  0:0043072  T 2  63420:2  T 1
0 hcp
0
GCoSi
Co:Co  GCo ¼ 20; 000
2 b 0 CoSi2
GSi:Si  0 GDiamond
Si ¼ 20; 000b
0
GCoSi 0 CoSi2 0 CoSi2 0 CoSi2
Si:Co ¼ GCo:Co þ GSi:Si  GCo:Si
2

(Si): (Co, Si)1

0
GDiamond
Co  Ghcp
Co ¼ 20; 000
b

a
Temperature (T) in Kelvin and Gibbs energy in J (mol atoms)1.
b
The underlined parameters are adjusted in the present work. The other parameters are taken from the recent evaluation [12].
 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950 3947

independent of concentration. In consequence, it is a good
approximation to set DGCo Si Co Si
Co ¼ DGCo and DGSi ¼ DGSi . The
finally obtained atomic mobility parameters of Co and Si in
(aCo), (eCo) and (Si) phase are listed in Table 3.
In the second step, the self-diffusion coefficients of Co
and Si in intermediate compounds are assessed. The self-
diffusion coefficients of Co and Si in the CoSi2 phase, as
well as that of Si in the CoSi phase, can be evaluated from
the experimental data of Barge et al. [41] and van Dal et al.
[16] via the Arrhenius equation. As pointed out by van Dal
et al. [16], Si is virtually the only mobile species in the CoSi
phase. Consequently, the self-diffusion coefficient of Co in
the CoSi phase is assumed to be 1/100 of that of Si in the
CoSi phase. Such an assumption proves to be reasonable in
the subsequent diffusion growth modeling of the CoSi
phase. Owing to limited experimental information, the
self-diffusion coefficients of Co and Si in the aCo2Si phase
are assumed to be equal to those of Ni and Si in the d (low-
temperature form of Ni2Si) phase of the Ni–Si system [10],
in view of the fact that aCo2Si and d have the same crystal
structure. All the evaluated self-diffusion coefficients of Co
and Si in the three intermediate phases are summarized in
Table 4.
Fig. 7a and b presents the calculated self-diffusion coef-
ficients of Co and Si as a function of inverse temperature,
compared with the experimental data [16–41]. As shown
in the figures, the calculated values are in excellent agree-
ment with the selected experimental data [16,23,26,37–39].
The good fit to the other experimental data [17–
22,24,25,27–36] proves that the assessed atomic mobility
parameters obtained in the present work are reliable.
In Fig. 8, the calculated inter-diffusion coefficients in the
(aCo) phase from 1000 to 1200 °C with an interval of 50 °C
are compared with experimental values from Yamamoto
et al. [51] and the present work. As shown in the figure,
the agreement between the calculated values and the exper-
iment ones >1050 °C is very good. Moreover, the extrapo-
lated curves at lower temperatures (1000 and 1050 °C)
based on the parameters obtained from the data at temper-
atures >1050 °C can also reproduce most of the experimen-
tal data. The fact that the extrapolated curve at 1050 °C is
located between the two sets of experimental data can also
verify the reliability of the present parameters obtained.
The largest difference between the two sets of experimental
inter-diffusion coefficients at 1050 °C does not exceed
100%. This is the typical experimental error associated with
the measurements of diffusivities in dilute solution regions.
The slightly concave shape of the extrapolated curves at
1000 and 1050 °C is due to the effect of magnetism, which
was considered in thermodynamic modeling [12].
Further validation of the atomic mobility parameters
obtained is performed by checking whether the parameters
can describe satisfactorily the experimental information
that was not used in the evaluation of the parameters.
Fig. 9 shows the model-predicted concentration profiles
of the Co/Co–10 at.% Si diffusion couple annealed at
1050 °C for 192 h, compared with the experimental data
obtained in the present work. The calculated result is in

Table 3
Summary of the atomic mobility parameters of Co and Si in (aCo), (eCo) and (Si) phases obtained in the present worka
Phases Mobility Parameters
4 0 Co;Si
(aCo) Mobility of Co DGCo Si
Co ¼ 296542:9  74:48  T , DGCo ¼ 286; 000  RT  lnð3:5  10 Þ, D GCo ¼ 288318:0 þ 69:75  T
4 1 Co;Si
Mobility of Si DGCo Si
Si ¼ 280658:2  70:14  T , DGSi ¼ 286; 000  RT  lnð7:0  10 Þ, D GSi ¼ 130597:8  128:76  T
4 0 Co;Si
(eCo)b Mobility of Co DGCo Si
Co ¼ 296542:9  74:48  T , DGCo ¼ 286; 000  RT  lnð3:5  10 Þ, D GCo ¼ 288318:0 þ 69:75  T
4 1 Co;Si
Mobility of Si DGCo Si
Si ¼ 280658:2  70:14  T , DGSi ¼ 286; 000  RT  lnð7:0  10 Þ, D GSi ¼ 130597:8  128:76  T
8 8
(Si) Mobility of Co DGCo Si
Co ¼ 269766:9 þ RT  lnð9:1  10 Þ, DGCo ¼ 269766:9 þ RT  lnð9:1  10 Þ

Mobility of Si DGCo Si
Si ¼ 457306:4  26:11  T , DGSi ¼ 457306:4  26:11  T
a 1
In J (mol atoms) ; temperature (T) is in Kelvin. The underlined parameters are estimated in the present work considering the limited experimental
data in the (aCo) phase, and the other parameters are assessed in the present work.
b
Owing to lack of experimental information, the mobility parameters of (eCo) phase are assumed to be equal to those of (aCo) phase.

Table 4
Summary of the self-diffusion coefficients of Co and Si in the intermediate phases of the Co–Si systema
aCo2Sib
 
4 3
DCo
aCo2 Si ¼ 3:0  10 expð161; 000=RT Þ, DSi
aCo2 Si ¼ 2:8  10 expð294; 000=RT Þ
CoSi
 
8 6
DCo
CoSi ¼ 3:2  10 expð206; 000=RT Þ,c DSi
CoSi ¼ 3:2  10 expð206; 000=RT Þ
CoSi2
 
4 8
DCo
CoSi2 ¼ 2:8488  10 expð296164:7=RT Þ, DSi
CoSi2 ¼ 2:8  10 expð186; 000=RT Þ
a
In m2 s1; temperature (T) is in Kelvin.
b
Owing to the lack of experimental data, the parameters of aCo2Si phase are assumed to be equal to those of d phase in the Ni–Si system [10].
c
The self-diffusion coefficient of Co in CoSi phase is supposed to be 1/100 that of Si in CoSi phase, taking into account the experimental information of
van Dal et al. [16].
3948 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950

Fig. 7. Calculated self-diffusion coefficients of (a) Co and (b) Si in various phases as a function of inverse temperature along with the corresponding
experimental data [17–40] according to the present mobility parameters. A constant, M, is added in order to separate the data for different phases in both
figures. The error bars for experimental data are shown in the figures in the cases they are reported in the literature.

Fig. 9. Model-predicted concentration profiles of the Co/Co–10 at.% Si

Fig. 8. Calculated inter-diffusion coefficients in (aCo) phase at various diffusion couple annealed at 1050 °C for 192 h, compared with the present
temperatures along with experimental data from Yamamoto et al. [51] and experimental data.
the present work.

accordance with the experimental data within experimental in the present work are used. For the analytical method,
error. Small discrepancies in the Co-rich side exist between the growth of CoSi phase in a bulk diffusion couple is gov-
modeling and experiment. The discrepancies can be traced erned by the following equations:
back to the differences between the measured and calcu- oC i =ot ¼ Dave 2 2
ði ¼ aCo2 Si; CoSi and CoSi2 Þ
i o C i =ox
lated inter-diffusion coefficients at 1050 °C, as shown in
ð8Þ
Fig. 7. Fig. 8 provides confirmation on the reliability of
the mobility parameters of the (aCo) phase. on1 =ot ¼ ðDave
aCo2 Si oC aCo2 Si =ox
Fig. 10 shows the model-predicted growth rates of CoSi 1
þ Dave 0
CoSi oCCoSi =oxÞ=ðC aCo2 Si  CCoSi Þ ð9Þ
phase in the aCo2Si/CoSi2 diffusion couples at 914, 1000
and 1100 °C along with measured data [16]. The solid lines on2 =ot ¼ ðDave
CoSi oC CoSi =ox
are calculated by means of DICTRA simulation, while the þ Dave 1 0
CoSi2 oC CoSi2 =oxÞ=ðC CoSi  C CoSi2 Þ ð10Þ
dotted ones are obtained using the analytical method.
Within estimated experimental errors, all calculations rea- The boundary conditions are C aCo2 Si ¼ C 0aCo2 Si ¼ constant
sonably reproduce the experimental data [16]. In the DIC- at x = 1 and C CoSi2 ¼ C 1CoSi2 ¼ constant at x = +1. As
TRA simulation, the moving boundary model [67] and the these intermediate compounds (aCo2Si, CoSi and CoSi2
average inter-diffusion coefficients of aCo2Si, CoSi and phases) have narrow homogeneity ranges, it is reasonable
CoSi2 phases based on the modified thermodynamic data to assume that the concentration profile within each phase
 L. Zhang et al. / Acta Materialia 56 (2008) 3940–3950
Fig. 10. Model-predicted and measured [16] thicknesses of the reaction
layer CoSi in aCo2Si/CoSi diffusion couples vs square root of time at
different temperatures. The solid lines are calculated by DICTRA software
[3], whereas the dotted lines are from the analytical method.
is linear at any time. This assumption yields zero for the
second derivative of composition C vs distance x. Conse-
quently, Eq. (8) may be ignored for growth description of
these intermediate phases. By solving Eqs. (9) and (10),
one can get the thicknesses of the CoSi phase at different
times and temperatures.
Some semi-corrections can be employed to verify whether
the atomic mobility parameters obtained are reasonable.
One [68–71] of the criteria for fcc crystals is expressed as
Q
¼B
RT fcc
M References
where Q is the activation energy for volume diffusion in the
fcc phase in J mol1, T fcc
M is the melting temperature of the
pure element in the fcc structure in Kelvin, and B is a con-
stant, which is 16–22 for the fcc phase [71]. The B value
calculated in the present work is 20.2, which is located in
the above numerical limit, and also agrees well with that
value of 19.5 reported by Campbell et al. [1].
The present work represents the first systematic investi-
gation for the atomic mobility in one whole binary system
with solution phases, stoichiometric compounds and inter-
mediate compounds showing noticeable homogeneities.
The key to the successful modeling of the diffusion phe-
nomena is the extension of the ‘‘average thermodynamic
factor” to model binary compounds with certain homoge-
neity ranges and the use of the first-principles calculation in
clarifying contradictory diffusion coefficients. A hybrid
approach of key experiments, the first-principles calcula-
tion and DICTRA assessments for effective establishment
of kinetic database of technologically important alloys is
thus highly recommended.
6. Conclusion
1. Based on the critical review of the experimental informa-
tion in the Co–Si system, key experiments in the bulk
3949
Co/Si and Co/Co–10 at.% Si diffusion couples were
performed in the present work. Meanwhile, the first-
principles calculations are conducted to clarify the
bewildering impurity diffusion coefficients of Co in Si.
2. On the basis of the reliable literature data and the pres-
ent work, self-consistent atomic mobility parameters of
both Co and Si in (aCo), (eCo), aCo2Si, CoSi, CoSi2
and (Si) phases are obtained. Comprehensive compari-
sons show that most of experimental data can be well
reproduced by the present description.
3. The successful description for the diffusion growths of
intermediate compounds in the Co–Si system shows that
the present approach is of general validity and applica-
ble to establish the kinetic database of technically
important alloys.
Acknowledgements
The financial support from the Creative Research
Group of National Natural Science Foundation of China
(Grant No. 50721003), the National Outstanding Youth
Science Foundation of China (Grant No. 50425103) and
the National Natural Science Foundation of China (Grant
No. 50571114) is acknowledged. One of the authors (Yong
Du) acknowledges the Cheung Kong Chair Professorship
released by the Minister of Education of China for finan-
cial support. The Thermo-Calc Software AB in Sweden is
gratefully acknowledged for the provision of Thermo-Calc
and DICTRA software.
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