Characterization of the diffusion properties of chromium in stainless-steel oxides by

photoemission spectroscopy
Boklae Cho, Sangwoon Moon, Sukmin Chung, Kijeong Kim, Taihee Kang, and Bongsoo Koo

Citation: Journal of Vacuum Science & Technology A 19, 998 (2001); doi: 10.1116/1.1368837
View online: http://dx.doi.org/10.1116/1.1368837
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 Characterization of the diffusion properties of chromium in stainless-steel
oxides by photoemission spectroscopy
Boklae Cho, Sangwoon Moon, and Sukmin Chunga)
Department of Physics, Pohang University of Science and Technology, Pohang, Kyungbuk 790-784, Korea
Kijeong Kim, Taihee Kang, and Bongsoo Koo
PLS, Pohang Accelerator Laboratory, Pohang University of Science and Technology, Pohang,
Kyungbuk 790-784, Korea
共Received 29 September 2000; accepted 12 March 2001兲
Characterization of diffusion properties of atoms in oxides is crucial for understanding oxidation
mechanism of metals because the oxidation is mediated by diffusion. Employing in situ
photoemission spectroscopy, we have observed diffusion-induced compositional variations of
stainless-steel surfaces during oxidations at 450 and 550 °C in the oxygen partial pressure range
1⫻10⫺9 – 1⫻10⫺5 Torr. Initially, a significant amount of metallic chromium was present at the
surface of stainless-steel oxide layers. During subsequent oxidation, thin oxide films grew on top of
the oxide layer, but there existed critical pressures below which the oxide film formed was almost
complete Cr2O3. From the critical pressures and growth rates of the oxide film, diffusion rates for
chromium through the oxide layer have been determined and a mechanism for the diffusion of
chromium in the stainless-steel oxide layer is proposed. © 2001 American Vacuum Society.
关DOI: 10.1116/1.1368837兴

I. INTRODUCTION pressure. Depending on the competition between oxidation

Oxidation of stainless-steel has been a subject of numer-
ous studies because the chromium-rich oxide film formed
protects the underlying bulk from corrosion.1 Recently,
vacuum thermal oxidation, which is based on the selective
oxidation of chromium at low oxygen partial pressures,2 has
attracted particular interests with reference to its potential
technological applications. The high resistance to
corrosion3,4 and sorption5 is mainly attributed to the ob-
served high chromium-enrichment in the surface film. At the
present time, the reaction mechanism between stainless-steel
and oxygen with low partial pressures is not well understood.
X-ray photoelectron spectroscopy and atomic force mi-
croscopy studies of an 18/8 stainless steel which was oxi-
dized at 450 °C in oxygen partial pressures of 1⫻10⫺9 to
1⫻10⫺4 Torr revealed that the composition and morphology
of the oxides formed were strongly affected by the oxygen
partial pressure.6 At oxygen pressures (p ⬘ ) around 10⫺8
Torr, there was a transition for which the outer oxide region
changed from rough iron-rich oxide to smooth chromium-
rich oxide. Similar trends were also observed by surface sen-
sitive photoemission spectroscopy 共PES兲.7,8 In particular, the
oxide film formed at p ⬘ ⫽1⫻10⫺9 Torr was almost com-
pletely Cr2O3.
An important feature of the Fe–Cr–O system is the exis-
tence of a critical pressure (p c⬘ ) of oxygen at specific sample
temperatures, where the supply of chromium and oxygen to
the gas/oxide interface are of an equal order of magnitude.
The supply of chromium towards the gas/oxide interface in-
creases with increasing temperature, while the supply of oxy-
gen towards the gas/oxide interface increases with increasing
a兲
Author to whom correspondence should be addressed; electronic mail:
smc@postech.ac.kr
temperature and oxygen pressure, therefore, the different ox-
ide phases may occur. At 450 °C, it was found that the num-
ber of chromium atoms reaching the gas/oxide interface per
unit time is equal to the number of dissociated oxygen atoms
adsorbing to the surface per unit time at p c⬘ around 10⫺8
Torr.5,8 Thus, if we assume that all adsorbed oxygen will
react with chromium only, there will form a pure chromium
oxide at 450 °C and p ⬘c ⬃1⫻10⫺8 Torr. At temperatures ex-
ceeding 450 °C and/or p ⬘ ⬍ p c⬘ , there will be a larger supply
of chromium from the alloy bulk to the gas/oxide interface
than of oxygen, and initially metallic chromium is present
but a pure chromium oxide is expected ultimately.5 At tem-
peratures below 450 °C and/or p ⬘ ⬎ p ⬘c , on the other hand,
the number of chromium atoms diffusing to the gas/oxide
interface is reduced to allow all oxygen to react only with
chromium which has higher free energy for oxide formation
than iron.9 Thus, more mobile iron,10 too, will segregate to
the gas/oxide interface to react with oxygen during further
oxidation. Hence, the film will become more enriched in
iron.
Since the critical pressure depends upon the flow of chro-
mium at the earliest stages of oxidation, it is of importance to
characterize the diffusion of chromium through the oxide to
the gas/oxide interface. However, the diffusion data are not
readily available. Diffusion studies of metals in stainless-
steel oxide or chromium oxide during oxidation have usually
been made in high oxygen pressures and high temperatures
where oxidation-induced changes of the oxide film are
conspicuous.11–13 Meanwhile, diffusion studies in low oxy-
gen pressures and medium oxidation temperatures 共⭐600 °C兲
were relatively few. The oxide film growth is so slow—⬃10
Å after 24 h oxidation at 450 °C in the oxygen partial pres-
sure of 1⫻10⫺9 Torr7—that investigation of vacuum ther-

998 J. Vac. Sci. Technol. A 19„3…, MayÕJun 2001 0734-2101Õ2001Õ19„3…Õ998Õ6Õ$18.00 ©2001 American Vacuum Society 998

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 999 Cho et al.: Characterization of the diffusion properties 999

mal oxidation needs very sensitive surface-analysis tools to

monitor during oxidation the compositional changes from
which the diffusion rates of metals can be extracted. In this
regard, PES using synchrotron radiation spells an optimum
choice to oxidation researchers. In addition to its very high
surface sensitivity, it can change its probing depth by tuning
photon energy, giving the distribution of species perpendicu-
lar to the surface in situ during oxidation.9
This work is an extension of previously published results
on stainless steel oxidized at 450 °C5,7,8 and includes samples
oxidized at 550 °C. Particular attention is paid to the effect
on the oxidation behaviors arising from the change of oxida-
tion temperature and oxygen partial pressure (p ⬘ ). The dif-
fusion property of chromium in stainless-steel oxide layer FIG. 1. Cr 3p 共obtained with h ␯ ⫽143 eV, surface sensitive兲 and Cr 2p
共obtained with h ␯ ⫽950 eV, bulk sensitive兲 spectra from the stainless steel
suggested by the oxidation characteristics is also discussed. surface annealed at 450 °C for 10 min.

II. EXPERIMENTAL METHOD
The substrate samples used for these experiments are a
commercial grade type 304 stainless-steel 共Nilaco corpora-
tion兲, where Cr is 17%–19%, Ni 8%–10%, Mn 2%, Si⬍1%,
Mo⬍0.6%, Fe balance. Each sample is a foil of about 0.1
mm thickness with surface area of 1⫻1 cm2. The thin foil
samples were chemically cleaned by immersion in BN
cleaner—a type of alkaline electrocleaner containing sodium
hydroxide and sodium silicate 共Novamax Tech. Inc.兲—
followed by rinsing in cold deionized water. The photoemis-
sion measurements were performed at the 2B1 spherical grat-
ing monochromator beamline at the Pohang light source
共PLS兲 at the Pohang Accelerator Laboratory. The base pres-
sure of the experimental chamber was 1⫻10⫺10 Torr and the
approximate partial pressure of hydrogen was below 5
⫻10⫺11 Torr. Maintaining the oxidation temperature at
550 °C, samples were oxidized in the analysis chamber by
heating the sample holder in oxygen pressures of 1
⫻10⫺7 – 1⫻10⫺5 Torr. The oxidation process was similar to
that of the previous oxidation experiments at 450 °C.5,7
Research-grade oxygen gas was leaked into the system and
the oxidation temperature was monitored with a chromel–
alumel thermocouple attached on the sample holder. We
used mainly a photon energy h ␯ ⫽143 eV 共surface sensitive兲,
for which the inelastic mean free path of photoelectrons from
Cr 3p states is about 6 Å,7 and partly a photon energy h ␯
⫽950 eV 共bulk sensitive兲, for which the inelastic mean free
path of photoelectrons from Cr 2p states is about 9 Å. The
overall instrumental resolution was about 0.4 eV at the pho-
ton energy h ␯ ⫽143 eV used. Background was removed
from the spectra using the Shirley method.14
oxygen partial pressure. At 450 °C, however, there were
some additional oxidation characteristics that were not pre-
sented previously.
At the early stages of oxidation, Cr 3p spectra showed a
clear metallic feature beside the oxide peak. Comparison of
PES spectra indicates that the metallic chromium existed
mainly on the surface. Figure 1 shows Cr 3p 共obtained with
h ␯ ⫽143 eV, surface sensitive兲 and Cr 2p 共obtained with
h ␯ ⫽950 eV, bulk sensitive兲 spectra from a stainless-steel
surface annealed in vacuum for 10 min. In the spectra, only
the surface-sensitive Cr 3p spectrum displays the metallic
chromium feature, suggesting that there was a considerable
migration of metallic chromium to the surface from the bulk
alloy during the vacuum annealing.
The growth rate of oxide film was strongly affected by the
oxygen partial pressure. Figure 2 shows the change of the
oxide film thickness as a function of time exposed to p ⬘
⫽1⫻10⫺9 Torr oxygen. The thickness was estimated by us-
ing the attenuation rate of the metallic chromium peak ob-
tained by calculating the core level area and the escape
length of photoelectron. The growth seems to be linear. For
the oxidation at 1⫻10⫺9 Torr oxygen pressure, the thickness
was 2.7 Å after oxidation of about 150 min and 10 Å after

III. EXPERIMENTAL RESULTS

A. Oxidation at 450 °C
The oxidation behaviors of stainless steel surface at this
temperature were described elsewhere in detail.5,7 In brief,
chromium-rich oxide films grew on top of the native oxide
layer as oxidation continued, but the composition of the ox- FIG. 2. The change of the thickness of oxide film as a function of time
ide film was significantly changed by the variation of the exposed to 1⫻10⫺9 Torr oxygen.

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 1000 Cho et al.: Characterization of the diffusion properties 1000

FIG. 3. Structure of stainless steel oxide at the final stage of oxidation.

about 1300 min. Figure 3 shows the structure of the oxide

film formed on the natural oxide layer at the final stage of
oxidation. At higher oxygen pressures, the oxide film grew in
a much faster rate. The thickness of the oxide film became
⬃10 Å after oxidation of about 30 and 90 min at p ⬘ ⫽1
⫻10⫺7 and 1⫻10⫺8 Torr, respectively.

B. Oxidations at 550 °C
At this temperature, general oxidation behaviors were
similar to those at 450 °C;5,7 lower 共higher兲 oxygen partial
pressure favored the formation of chromium-rich 共iron-rich兲
oxide film as shown in Figs. 4 and 5. For the as-introduced
sample surface, the 3p peak of iron-oxide whose binding
energy is 55.8 eV was a dominant feature whereas the peaks
of chromium, manganese, nickel, and sodium oxides were
relatively small. As the oxidation continues at p ⬘ ⫽1
⫻10⫺7 Torr, chromium oxide becomes the main constituent
with trace iron, manganese, and sodium oxides. The oxida- FIG. 4. The evolution of Cr, Fe, and Mn 3p core-level PES spectra at 550 °C
tions at p ⬘ ⫽1⫻10⫺6 and 1⫻10⫺5 Torr showed somewhat with vacuum annealing and subsequent oxygen exposure in an oxygen par-
different results. A change in the chemical composition of tial pressure (p ⬘ ) of 1⫻10⫺7 Torr 共a兲, 1⫻10⫺6 Torr 共b兲, and 1⫻10⫺5 Torr
the native surface layer of the steel during oxidation is 共c兲.
clearly visible. Figures 4 and 5 show that the iron-oxide layer
is replaced by a chromium-oxide film and becomes the domi-
nant feature. In Fig. 4, one can find that there exists a sig- mium and diffusion rates depend exponentially on tempera-
nificant amount of iron oxide on the surface. ture, the increase of p c⬘ with rise of oxidation temperature is
Comparison of PES spectra, however, shows that the criti- readily expected.
cal oxygen partial pressure at 550 °C is an order of magni-
tude higher than that (p c⬘ ⫽⬃1⫻10⫺8 Torr兲 at 450 °C. Fig- IV. DISCUSSION
ure 6 shows that the PES spectra from the surfaces fully
oxidized in oxygen of 1⫻10⫺7 Torr at 550 °C and in oxygen A. Diffusion mechanism of chromium in stainless-
steel oxide layer
of 1⫻10⫺9 Torr at 450 °C resemble each other; only trace
Fe 3p peaks are observed in the spectra. Meanwhile, the Oxidation of stainless-steel alloy usually shows very com-
spectra from the surfaces fully oxidized in oxygen of 1 plicated kinetics that is far from understanding, especially at
⫻10⫺6 Torr at 550 °C and in oxygen of 1⫻10⫺7 Torr at medium temperatures around 500 °C. Wild12 reported a para-
450 °C look very similar to one another, showing conspicu- bolic growth of oxide film at ⭓500 °C, but Driscoll et al.15
ous Fe 3p peaks. From this discussion, the critical pressure proposed that logarithmic oxidation kinetics was operating at
( p c⬘ ) can be inferred: ⬃5⫻10⫺7 Torr at 550 °C. Considering 300 °C. Young et al.16 also showed that the oxidation of
that the critical pressure (p c⬘ ) is the oxygen pressure at which polycrystalline chromium in the range 300⭐T⭐600 °C was
the supply of oxygen slightly exceeds the diffusion of chro- characterized by an abrupt transition in kinetic behavior and

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 1001 Cho et al.: Characterization of the diffusion properties
FIG. 5. The change of the relative amount of Cr, Fe, and Mn at 550 °C depending on the oxidation pressure at 共a兲 1⫻10⫺5 Torr, 共b兲 1⫻10⫺6 Torr, and 共c兲
1⫻10⫺7 Torr, respectively.
the pretransition kinetics was logarithmic. In the logarithmic
oxidation kinetics, migration of atoms need electric field
arising from the adsorbed oxygen anions on the surface.17,18
The spectra in Fig. 1, however, show the presence of surface
metallic chromium atoms that have migrated from the bulk
alloy during the annealing in vacuum although the annealed
surface have never experienced oxygen exposure, suggesting
that the migration mechanism of chromium may be a pure
diffusion during the vacuum thermal oxidation.
The presence of surface metallic chromium indicates also
the operation of a pipe diffusion mechanism19 共diffusion
along high diffusion paths such as dislocation or grain
boundaries兲 during the oxidation. As depicted in Fig. 7, the
pipe diffusion in the stainless-steel oxide layer may find its
FIG. 6. Comparison of PES spectra from the stainless steel surfaces fully
oxidized at 450 °C and 550 °C.
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1001
analogy in gas movement via many long narrow pipes that
connect two boxes. The large box, small box, gas, and pipes
represent the underlying bulk alloy, surface, migrating chro-
mium atoms, and high diffusivity paths in the oxide layer,
respectively. At the outset, the surface 共small box兲 is vacant
of chromium atoms 共gas molecules兲. After the onset of an-
nealing, chromium atoms migrate along the high diffusivity
paths 共pipe兲 from the bulk area 共large box兲, but as soon as
they reach the surface 共small box兲 they spread out fast be-
cause migration is usually fastest on the surface in solids.19
Since the volume of high diffusivity paths is usually very
small, however, only small amount of metallic chromium
can be between the bulk alloy and the surface. If a pipe
diffusion mechanism is working, therefore, the surface
FIG. 7. Schematic diagram of a model for chromium diffusion through grain
boundary in the oxide layer of stainless steel.
 1002 Cho et al.: Characterization of the diffusion properties 1002

should show an enrichment of metallic chromium, which is

clearly observed in Fig. 1. On the other hand, if chromium
atoms migrate through volume diffusion 共diffusion through
entire lattice兲, there should be a concentration gradient along
the oxide layer and the amount of metallic chromium will
decrease near the surface. In this regard, high diffusivity
paths may be considered as the diffusion route for chromium
atoms during vacuum thermal oxidations. Considering that
the oxide layer is composed of grains,6,8 we propose that
grain boundaries in the oxide layer may be the high diffusiv-
ity paths.

B. Determination of diffusion rates for chromium

The oxidation of stainless-steel at high temperatures re- FIG. 8. Comparison of diffusion constants.
sults in the rapid formation of the oxide film mostly leading
to a chromium depletion in the zone next to the oxide film
because of the limited supply of chromium from the bulk
atoms cm⫺2 s⫺1 at p ⬘ around 1⫻10⫺8 Torr. So, the sticking
alloy to its surface region. In that case, diffusion in the bulk
coefficient of oxygen was found to be of the order of 0.15, a
alloy becomes the rate-limiting step for the oxide film
value which is close to that observed during initial oxidation
growth. The measurements performed in this and previous
of pure chromium.20
experiments,7 however, showed no measurable chromium-
Since depletion zone of chromium was not observed, the
depleted zone. Other vacuum thermal oxidation studies by
chromium concentration at the metal/oxide interface is esti-
Hultquist et al.2 and Ohmi et al.3 also reported that depth
mated to be equal to that in type 304 stainless-steel alloys,
profiles did not reveal any depletion region near the metal/
that is 1.64⫻1022 atoms cm⫺3. Assuming that the concentra-
oxide interface, suggesting that chromium atoms can diffuse
tion of metallic chromium is zero at the oxide film/oxide
fast enough in the underlying metal. So the diffusion of chro-
layer interface and that the oxide layer thickness is ⬃50 Å 共a
mium, not in the bulk alloy but in the natural oxide layer,
typical thickness of stainless-steel natural oxide layer兲, dc/dx
was the rate-limiting step for the oxide growth. Then the
can be calculated from
growth rate of an oxide film reflects the diffusion rates of
chromium in the oxide layer as long as the rate of arrival of dc 共 c 1 ⫺c 2 兲
oxygen on the surface is fast enough, i.e., p ⬘ ⭓p ⬘c . Because ⫽ , 共4兲
dx d
significant amount of iron oxide appeared in oxide films at
where c 1 is the concentration of metallic chromium at the
p ⬘ ⬎p ⬘c , however, only the growth rates at p ⬘c were used for
metal/oxide interface, c 2 the concentration at the oxide film/
determining the diffusion rate of chromium.
oxide layer interface, and d the thickness of the oxide layer.
According to Fick’s first law of diffusion, the flux of dif-
From the above J Cr and dc/dx, the diffusion rate of chro-
fusing atoms is given by
mium can be obtained
dc
J⫽D . 共1兲 D Cr⫽2.30⫻10⫺17 cm2 s⫺1 at 450 °C. 共5兲
dx
Considering the critical pressure p c⬘ of 5⫻10⫺7 Torr at
Here J is the flux, D the diffusion constant, and c the con- 550 °C, the diffusion rates of chromium at 550 °C was ob-
centration. At the completion of oxidation in 1⫻10⫺8 Torr, tained by assuming that the sticking coefficient of oxygen is
p c⬘ at 450 °C, a rate increase in oxide thickness of 1.85 the same for both the temperatures
⫻10⫺11 cm s⫺1 resulted. The oxide formed is of the type
Cr2O3, whose molecular number density is 2.06⫻1022 D Cr⫽1.15⫻10⫺15 cm2 s⫺1 at 550 °C. 共6兲
molecules cm⫺3 representing total chromium flux Substituting these values in the diffusion equation yields

冉 冊
⫺2 ⫺1
J Cr⫽7.62⫻10 atoms cm
11
s . 共2兲 193.4⫻103
D Cr⫽2.17⫻10⫺3 exp ⫺ cm2 s⫺1. 共7兲
We use the kinetic theory of gases giving the number of RT
molecules incident on the unit area of surface per second 共⌫兲
Diffusion rates calculated from Eqs. 共5兲 and 共6兲 are in
as a function of pressure 共p兲, temperature 共T兲, and mass 共m兲
general agreement with previously reported values at higher
according to
temperatures, as shown in Fig. 8, and the activation energy is
p close to that 共255 kJ兲 in a hot-pressed chromium oxide but
⌫⫽ . 共3兲 much lower than that 共415 kJ兲 in a sintered oxide. Kofstad
共 2 ␲ mkT 兲 1/2
and Lillerud11 explained for the energy difference between
At the oxide/gas interface, it is then found that the rate of the two types of oxides that the hot-pressed oxide contained
arrival of oxygen atoms is approximately 7.17⫻1012 numerous high diffusivity paths in which the activation en-

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 1003 Cho et al.: Characterization of the diffusion properties 1003

ergy for chromium migration is much lower than that in the VMT. Experiments at PLS were supported partly by Minis-
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V. CONCLUSION 4
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7
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10
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ACKNOWLEDGMENTS 17
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18
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This work was supported partly by the Korea Science and 19
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