Photoreduction of Hexavalent Chromium during X-Ray

Photoelectron SpectroscopyAnalysis of Electrochemical

and Thermal Films
Gary P. Halada and Clive R. Clayton*
Department of Materials Science and Engineering, State University of New York at Stony Brook,
Stony Brook, New York 11794-2275

ABSTRACT
Cr spectra obtained by x-ray photoelectron spectroscopy (XPS) of corrosion product layers is critically e x a m i n e d for
evidence of photoreduction of hexavalent species. Tetravatent and trivalent decomposition products are identified, and
methods of curve fitting and analysis are discussed. Disagreement between x~ray absorption near end structure and X P S
data, and b et ween t h e r m o d y n a m i c analysis and X P S data lead to the acceptance of a model for photoreduction of Cr 6+
based primarily upon core photoemission.

Chromium, as a major alloying element in corrosion re- In this study we address problems in XPS analysis of
sistant alloys, has been the subject of numerous analytical oxide films formed by various methods in Cr containing
studies. The purpose of such studies has often been to de- systems. We will show that the difficulty in observing max-
termine the role Cr plays in the formation of oxidized spe- imal valence species of Cr by XPS in electrochemically
cies which m ay act as a surface barrier to further com- formed corrosion product layers is similar to the reported
bined electrochemical or chemical reaction. The difficulty in X P S observation of hexavalent Cr in thermal
usefulness of x-ray photoelectron spectroscopy (XPS) in oxide films, caused by reduction processes which wilt be
characterizing the top one to fifteen atomic layers has led discussed in detail.
many groups, including this laboratory, to use it as a
means of determining the oxidation state of Cr in corro- Experimental
sion product layers formed on Cr containing alloys and All X P S measurements were performed with a V.G. Sci-
pure Cr.
entific ESCA 3 Mk.II spectrometer controlled by a V.G.
In X P S of anodie films formed on 304 stainless steel in 1000 data system. The entrance and exit slit widths for the
sulfuric acid, we have previously found a Cr-rich surface hemispherical analyzer were 4 m m resulting in a half angle
layer based upon trivalent Cr [in the form of Cr203 and for photoelectron emission of 0.095 radians. Photoelectron
Cr(OH)a], with a minor contribution from hexavalent Cr (as take off angles reported for variable angle X P S were meas-
CrO3 and CrO]-) (1). The presence of chromate was sug- ured with respect to the sample surface and were chosen
gested to result from c h r o m i u m hydroxide reacting in the to enhance surface sensitivity and detectability of hexa-
solid state with excess lattice water. In this and subse- valent species in surface layers. A MgKel,2 (1253.6 eV)
que n t studies (2-5), the hexavalent chromate was found to x-ray source and a 20 eV pass energy were used for all anal-
serve as a cation-selective species, inhibiting the ingress of ysis providing a FWHM for the Audfv2 singlet of 1.25 eV.
anionic species (such as C1 ) which cause pitting and en- Base pressures during analysis were about 1 x 10 -9 tort.
hancing the deprotonation of the hydroxide surface layer. For reference, the binding energy of the AudfT/2 singlet was
Hence the oxide barrier layer is thickened and the resis- found to be 83.8 eV and that of the Cu2p3/2 singlet was
tance of the film to ingressing species is further improved. found to be 932.4 eV. All binding energies referred to in
Support for the occurrence of such solid-state reactions this paper, including those taken from the literature, were
within corrosion product layers was also provided by evi- corrected for charge shifting by referencing to the C l s line
dence of Green Rust I [Fe0.gFea.6 3+ 2. (O, OH, C1)9] and II
from the adventitious carbon at 284.6 eV. All data were
[4Fe(OH)2 9 2Fe(OH)3 9 FeSO4 9 xH20] in the film, species smoothed utilizing a nine-point quadratic/cubic least
which are predicted to be unstable in acidic solution and squares program following the m e t h o d developed by Sav-
which m u s t form from a topotactic reaction involving itsky and Gotay (16), which has been modified by Sher-
Fe(OH)2 (6). F u rt h er work showed evidence of the reduc- wood (18) to cover the truncation errors at the end of the
tion of the hexavalent species with time of exposure to spectra. The cttrve fitting program allowed the operator to
Mgt(al.2 radiation, with the appearance of decomposition synthesize peaks by specifying the peak's position, height,
products. Four hundred minutes of exposure brought width, and shape. The shape parameters included the
about a nearly complete reduction of Cr s+ (1). The reduc- peak's Gaussian/Lorentzian ratio and tail characteristics
tion of hexavalent Cr during X P S analysis has been noted such as height, slope, and exponential-to-linear tail mix.
by a n u m b e r of authors (7-11). In all cases the only The Ks', K(~3, and K~4 satellites were automatically in-
breakdown product discussed was the sesquioxide Cr203. cluded in the synthesis. A Shirley background subtraction
In our previous work on photoreduction in thermal oxides (19) was also conducted for each multiplet in the spectral
formed on Cr, a tetravalent reduction product, CrO2, was region under analysis. Since curve fitting can provide sev-
found (12). The binding energy of the reduction product eral solutions to the same spectrum, variable angle X P S
was the same as that for the decomposition product in the data, peak subtraction, double differentiation, and meas-
anodic oxide formed as part of the earlier study (1, 2). u r e m e n t of spin-orbit splitting were employed in order to
Hexavalent Cr as a species in thermal oxides on Cr has determine best fit. Peak subtraction was conducted fol-
been noted in a few studies using techniques such as wet lowing peak height normalization and nonlinear back-
chemical anaIysis (13), diffuse reflectance spectroscopy ground subtraction. In addition, selected spectra were aria-
(14), and x-ray absorption near-end structure (XANES) lyzed using an automated, incremental peak synthesis
(15); however, most X P S studies have failed to note the program which varied the peak height within an envelope
presence of hexavalent Cr in high-temperature oxide over a complete range in order to determine the best fit
films. Most often trivalent species alone were reported. Re- (checked through the chi-squared value) to the smoothed
cently, in a separate study, we addressed the photore- data. This process aided in the confirmation of fits by re-
duetion of hexavalent Cr in thermal oxide films formed on moving any peak which could be compensated for by a
Cr (16). corresponding increase in the height of neighboring
9 Electrochemical Society Active Member. peaks.

J. Electrochem. Soc., Vol. 138, No. 10, October 1991 9 The Electrochemical Society, Inc. 2921
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 2922 J. Electrochem. Soc., Vol. 138, No. 10, October 1991 9 The Electrochemical Society, Inc.

Table I. Fitting parameters for Cr2p~/2 peaks.

B.E. FWHM Gaussian/ Tail ht. Slope Tail mix

Peak (eV) (eV) Lorentzian (%) exp. (%)

Cr(met) 574.1 1.4 0.65 0.1 0.05 0.5

CrQ 575.2 1.7 0.85 0.1 0.07 0.5
Cr~O~ 576.3 2.4 0.50 0.001 20~ 0.5
CrOOH 577.0 2.2 0.50 0.001 20~ 0.5
CrO~ 578.3 1.4 0.50 0.001 20~ 0.5
CrO~- 579.3 1.4 0.50 0.001 20~ 0.5

A value of 20 for slope exponential indicates no tail.

Note: Since the choice of tail parameters will affect the actual FWHM of a peak, the software employed in this study uses one-half of the
value given and applies it only to the leading edge side of the peak being fitted.

All m e t a l l i c s a m p l e s for a n a l y s i s w e r e m e c h a n i c a l l y pol- of a t r i v a l e n t Cr s i g n a l or t h r o u g h p h o t o r e d u c t i o n of t h e te-

i s h e d u p t h e g r a d e s s t a r t i n g w i t h 600 grit silicon c a r b i d e t r a v a l e n t Cr.
p a p e r a n d f i n i s h e d w i t h a 0.25 ~ m d i a m o n d polish. I n situ S t a n d a r d s p e c t r a m a y b e e n h a n c e d t h r o u g h - p e a k sub-
o x i d i z e d s a m p l e s w e r e e t c h e d for 30 s w i t h 2.5 k e V K r § s t r a c t i o n of c o n t a m i n a n t species. F i g u r e 1 s h o w s s u b t r a c -
ions b e f o r e o x i d a t i o n . All s a m p l e s w e r e u l t r a s o n i c a l l y t i o n of t h e Cr2p3/2 s p e c t r a of s e s q u i o x i d e p o w d e r f r o m t h e
r i n s e d i n a c e t o n e , p r o p a n o l , a n d d o u b l y d i s t i l l e d w a t e r be- d i o x i d e p o w d e r . T h e d i f f e r e n c e s p e c t r a give a m o r e accu-
fore e l e c t r o c h e m i c a l t r e a t m e n t or in situ o x i d a t i o n . Polar- r a t e i d e a of t h e w i d t h a n d b i n d i n g e n e r g y of t h e t e t r a v a l e n t
i z a t i o n w a s c a r r i e d o u t in a c o n v e n t i o n a l G r e e n e cell (20) Cr2p3/2 singlet. E x c e s s i n t e n s i t y o n t h e h i g h b i n d i n g
u s i n g 0.5M H~SO4 (in t h e c a s e of t h e p a s s i v e film o n 19-9 e n e r g y side is a r e s u l t of r e d u c t i o n to C r O O H as m e n t i o n e d
s t a i n l e s s steel) or 0.16M Na~CrO~ p l u s a p H 8.4 b u f f e r solu- earlier. Tail p a r a m e t e r s w e r e a s s i g n e d s i m i l a r to t h o s e of
t i o n o f s o d i u m b o r a t e a n d b o r i c acid (in t h e case of t h e metallic chromium. Given the high electrical conductivity
c h r o m a t e d F e samples). I n b o t h cases, s a m p l e s w e r e ca- of t h e d i o x i d e , a s c a t t e r i n g p a r a m e t e r s i m i l a r to t h a t of m e -
t h o d i c a l l y p r e t r e a t e d in o r d e r to r e d u c e t h e p o l i s h f o r m e d tallic Cr is a s s u m e d . S p e c t r a f r o m h i g h v a l e n c y s t a n d a r d s
film. T h e 19-9 s t a i n l e s s s t e e l w a s p r e t r e a t e d at - 9 0 0 m V w e r e r e c o r d e d w i t h s h o r t x - r a y e x p o s u r e t i m e s to l i m i t re-
( s a t u r a t e d c a l o m e l e l e c t r o d e , SCE) for 15 r a i n in t h e sul- d u c t i o n to l o w e r v a l e n c e species.
furic a c i d s o l u t i o n . T h e F e w a s p r e t r e a t e d i n t h e b o r a t e F i g u r e 2 s h o w s a c u r v e fit for Cr2p3/2 s p e c t r a o b t a i n e d
b u f f e r s o l u t i o n a l o n e (before c h r o m a t e a d d i t i o n ) at f r o m a F e l 9 C r alloy w h i c h w a s o x i d i z e d for 1 h in 0.1 t o r r
- 8 4 6 m V for 15 rain. T h e c a t h o d i c c u r r e n t d u r i n g p r e t r e a t - o x y g e n at 450~ a n d t h e d o u b l e d i f f e r e n t i a t i o n of t h e spec-
m e r i t of F e s t a b i l i z e d at 20 t~A/cm ~. All s o l u t i o n s w e r e de- tra. T h e p r o m i n e n t p e a k s in t h e d o u b l e d i f f e r e n t i a t i o n cor-
a e r a t e d b y p u r g i n g w i t h A r for a t l e a s t 2 h, a n d all experi- r e s p o n d to c h a n g e s i n s l o p e for t e t r a v a l e n t , t r i v a l e n t , a n d
m e n t s w e r e p e r f o r m e d at r o o m t e m p e r a t u r e (22~ h e x a v a l e n t species. T h e s i n g l e p e a k at 576.7 eV is a r e s u l t
P o t e n t i a l s w e r e m e a s u r e d a g a i n s t a s a t u r a t e d c a l o m e l elec- of t h e close p r o x i m i t y of t h e s e s q u i o x i d e a n d h y d r o x i d e
trode. F o l l o w i n g t h e a n o d i c p o l a r i z a t i o n t r e a t m e n t , t h e p e a k s as well as t h e s m a l l size of t h e latter. S p i n o r b i t split-
s p e c i m e n s w e r e r e m o v e d f r o m t h e cell, w a s h e d w i t h de- t i n g a n d area r a t i o s of Cr2p3~2 to Cr2p~/2 s i n g l e t s h a v e also
a e r a t e d d o u b l y d i s t i l l e d w a t e r , d r i e d i n Ar, a n d m o u n t e d b e e n t a k e n i n t o a c c o u n t i n fitting a n d are g i v e n in T a b l e II.
o n t o a n X P S s a m p l e h o l d e r a n d t r a n s f e r r e d i n t o t h e spec-
t r o m e t e r . T h e e n t i r e p r o c e d u r e w a s c a r r i e d o u t i n a n Ar-
p u r g e d g l o v e b o x to r e d u c e t h e p o s s i b i l i t y of s u r f a c e re-
duction during transfer.
o
a

Curve Fitting and Analysis I

T h e m e t h o d o l o g y a n d p o t e n t i a l p r o b l e m s w i t h c u r v e fit- o

t i n g a n d d e c o n v o l u t i o n o f X P S C r s p e c t r a n e e d to b e d e a l t
w i t h as a s e p a r a t e i s s u e b e f o r e t u r n i n g to t h e r e s u l t s of o u r
analysis. S i n c e w e are e x a m i n i n g s p e c t r a w h i c h are a l t e r e d
a & l ~ 9
d u r i n g X P S a n a l y s i s , it is n e c e s s a r y to e x a m i n e c r i t e r i a b y Cr2p ,.'e ~ ". .:.: I
Q

w h i c h p e a k s a r e a s s i g n e d . X P S s p e c t r a p r e s e n t e d in t h i s
s t u d y are t h a t of t h e 2p~/~ e l e c t r o n s u b o r b i t a l of Cr. T h e
b i n d i n g e n e r g i e s a n d p e a k fitting p a r a m e t e r s d e r i v e d f r o m
I
t' "9 -": I
:'. ~ ""
o u r a n a l y s i s o f p o w d e r s is g i v e n i n T a b l e I. T h e s e s q u i o x - / Dioxide". .: : ' "
ide p o w d e r s t a n d a r d w a s p r e p a r e d t h r o u g h in situ h e a t i n g
and ion bombardment of commercially available powder
to r e d u c e a n y h i g h e r v a l e n c y c o n t a m i n a n t s . T h e C r Q
standard was created by a high-pressure method detailed
e l s e w h e r e (12) a n d a n a l y z e d f o l l o w i n g in situ s c r a p i n g to
e x p o s e a c l e a n surface. A s m a l l a m o u n t of u n r e a c t e d CrO3
w a s o b s e r v e d b y X P S a n d s y n c h r o t r o n X A N E S a n a l y s i s to
r e m a i n i n t h e p o w d e r . T r i v a l e n t c o n t a m i n a n t s are a p r o b a -
ble r e s u l t o f t h e r e a c t i o n of t r a c e w a t e r i n t h e v a c u u m sys- . %.~: . 9 ~
t e m w i t h t h e d i o x i d e . T h i s l e a d s to t h e f o r m a t i o n of
CrOOH, as h a s b e e n s h o w n b y K r a k o w et al. (21). T h e
Cr2p~/~ b i n d i n g e n e r g y of C r O O H is a p p r o x i m a t e l y t h e # .
s a m e as t h a t o f Cr(OH)~. T h i s w a s c o n f i r m e d b y X P S analy-
sis of c l e a n CrO~ c r u s h e d in A r a n d e x p o s e d to distilled i a

water. D i s c r e p a n c i e s i n t h e l i t e r a t u r e i n v o l v i n g t h e b i n d -
i n g e n e r g y o f CrO~ m a y b e c r e d i t e d in p a r t to t h i s passi- j. g
o

v a t i n g o x y - h y d r o x i d e layer. F o r e x a m p l e , F e v e et al. re- o o

p o r t e d a Cr2p~/e b i n d i n g e n e r g y of 577.2 e V for CrO~, a

..-~" Difference dlt

v a l u e close to t h a t of t h e h y d r o x i d e . C i m i n o et al. (11) re-

p o r t e d a b r o a d CrOe p e a k w i t h t h e s a m e b i n d i n g e n e r g y as . . . . . . . . . . . . . . . . . . . . . . . . T
5 9 5 ~ 9 3 $9~ ~ s 9 5 s 7 s s 5 ~ s a ~s~ ~ 7 9 ~77 5 7 5 5 7 3 ~7
CreO~ a n d m e n t i o n e d t h a t s o m e c o n t a m i n a n t m a y h a v e
Binding Energy
b e e n p r e s e n t . T h o u g h I k e m o t o ' s v a l u e (22) o f 576.1 e V
c o m e s c l o s e r to o u r value, r e a c t i o n w i t h c o n t a m i n a n t Fig. 1. Peak subtraction of Cr2p3/2 spectrum of dehydrated sesquiox-
water may have raised the binding energy by the addition ide from that of a chromium dioxide standard.

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 J. Electrochem. Soc., Vol. 138, No. 10, O c t o b e r 1991 9 The Electrochemical Society, Inc. 2923

; 9 9
.j

, \

! '
5~0 57~ 57~ 574
58N 5eo 57~ 57~ ~74 57~ B~ding Energy
Binding Energy
Fig. 3. Variation in Cr2p3/2 spectra from Fe passivated in 0,16M
Fig. 2. Cr2p312 spectra of Fe-19Cr oxidized for 1 h in flowing 02 and Na2Cr04 plus borate buffer for 1 h at 165 rnV with x-irradiation times
double differentiation of spectra showing major inflections. (Take off of (a) 40 rnin and (b) 5 h. Peak identification; 1, Cr042-; 2~ Cr03; 3,
angle = 20~ Peak identification: 1, Cr03; 2, CrOOH; 3, Cry03; and 4, CrOOH; 4~ Cr20~; S, Cr02.
Cr02.

tively. The film was formed at a potential of 100 mV in 1 h

Results of Analysis following the !5 rain cathodic pretreatment. Once again
Figure 3 shows x-irradiation damage during X P S analy- the hexavalent species is seen to decrease in area with a
sis of the Cr2p3/2 spectra of Fe passivated in 0.16M Na2CrO4 corresponding increase in the area of the tetravalent de-
added to a borate buffer for 1 h at 165 mV SCE. Following composition product singlet. Peak areas are given in
pretreatment in the borate buffer, the cell was entirely Table IV as a percentage of the overall multiplet area. Fig-
replenished with the chromate containing solution. Chro- ure 5a shows the Cr2p3/2 singlets for a passive film formed
mate on the surface, in the form of Cr2(CrO4)3 was found to on Fel9Cr9Ni following 45 rain and 6.5 h irradiation times
enhance deprotonation of the surface hydroxide resulting plotted on the same set of axes. The change in the peak en-
in a thicker sesquioxide barrier layer. This in turn leads to velope due to photoreduction is more apparent in the dif-
greater inhibition of pitting of Fe following the addition of ference spectra, 5b, which represents the subtraction of
NaC1 to the solution (23). This inhibition is partially caused the 45 min spectrum from the 6.5 h spectrum. The separa-
by the cation selective properties of the chromate formed tion between the binding energy of the peak on the low
on the surface, as has been noted in this group's earlier binding energy side of the difference spectrum and that of
work (2-5), and partially by the formation of a Cr 3+ barrier the base of the trough on the high binding energy side of
layer. Figure 3a shows the Cr2p3/2 spectra after 40 min the spectrum is equivalent to the difference in binding
MgK~ x-irradiation, and Fig. 3b shows the same region energies of the Cr2p3/2 singlets for C r Q and CrO3, respec-
after 5 h x-irradiaUon. The decrease in the hexavalent sig- tively (3.1 eV). The loss in area from reduced high valence
nal and the corresponding increase in the peak areas of species is approximately equivalent to the gain in area of
singlets belonging to decomposition products (Cr 4+, Cr 3+) the low binding energy decomposition product species.
is accounted for in Table III, which gives the peak areas The Cl s X P S spectra (shown in the inset in Fig. 5), corre-
for the figure as a percentage of the overall multiplet area. sponding to the 45 rain and 6.5 h Cr spectra, indicate some
slight narrowing (due to an increase in adsorbed contam-
Figures 4a and b display the Cr2p3/2 spectra for the pas- inant carbon species with a Cls binding energy of
sive film formed on Fel9Cr9Ni in 0,5M sulfuric acid solu- 284.6 eV) but no charge shifting with time.
tion following 45 min and 6,5 h exposure times, respec-

Table Ill. Peak areas from Cr2p3~ reduction spectra of chromated

Table II. Cr2p spin orbit separations and area ratios. pure Fe.
Species: Cr2p3/2-Cr2p!/2
splitting Cr2p3/2-Cr2pl/~
ratio Peak areas as fraction of multiplet
Species 40 min 5h
Cr (metal) 9.2 1.8
CrO2 9.5 2.0
Cr~O.~ 9.7 1.8 CrO~ 13.0 16.3
Cr(OH)3 9.7 1.8 Cr203 58.9 57.8
CrOOH 9.7 1.7 CrOOH 15.4 21.4
CrO3 9.2 2.6 CrO3 3.0 1.4
CrO~ 9.2 2.6 CrO~ 9.7 3.1

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 2924 J. Electrochem. Soc., Vol. 138, No. 10, October 1991 9 The Electrochemical Society, Inc.
=,,,
.:'.~.'~;
r"
2...+. (a)
Cls :: ""
~
:. ~'...
"." 6.5 hrs.
.~. o. §

/.
+ .!/ §
/ §
45 ~al. +4" "9

# :.- + .m* § .

+ 9
3 2"
t_ 9 I" "r

3.1eV . "
N
=[! -.... "
(b)
%

"".---.... _ _ --"%~._.-"~
m~ ~ d" ss

I
i
!
% 9 i Difference
....: spectra
| .

583 5~t 579 577 575 573

5~0 578 57S 57~4
Binding Energy
Binding Energy
Fig. 5. (a) Cr2p312 spectra from a passive film formed on Fe19CrNi
Fig. 4. Variation in Cr2p3:2 spectra from passive film formed on alloy in 0.SM H2S04irradiated with x-rays for times shown and (b), the
Fel9Cr9Ni alloy in 0.5M H2S04irradiated with x-rays for (a) 45 min spectra resulting from the subtraction of the short irradiation time peak
and (b) 6.5 h. Peak identification: 1, CrO~-; 2, Cr03; 3, CrOOH; 4, from the long irradiation time peak. Inset shows corresponding Cls
Cr203; 5, Cr02; 6, Cr (metal). spectra.

I n o r d e r to f u r t h e r d e m o n s t r a t e t h e effects o f p h o t o r e - small (on the order of the heat of adsorption of oxygen).

Revesz and Kruger (25) in later work noted that the stand-
d u c t i o n , w e i n c l u d e t h e r a d i a t i o n r e d u c t i o n of a t h e r m a l
o x i d e f o r m e d o n p u r e Cr i n 1 h at 400~ in 0.1 t o r r h i g h pu- ard free enthalpies of CrO3 and Cr203 are -141 and
-136 kcal real -I, respectively, and because the values are
rity o x y g e n in t h e s p e c t r o m e t e r . F i g u r e s 6a-c s h o w t h e ef-
so close, the phases are likely to coexist under nonequi-
fect of i r r a d i a t i o n t i m e o n t h e Cr2p3/2 s i n g l e t p e a k areas.
librium conditions. The absence of detection of C: + in
T h e s e d a t a are s h o w n n u m e r i c a l l y i n T a b l e V. T h e a m o u n t
of t e t r a v a l e n t Cr is s e e n to p e a k a f t e r a c e r t a i n a m o u n t of many XPS studies of electrochemical or thermal oxides is
i r r a d i a t i o n t i m e a n d t h e n d r o p s l o w l y d u e to r e d u c t i o n b y most likely due to (i) the small amounts of hexavalent Cr
r e a c t i o n w i t h t r a c e w a t e r v a p o r or g r a d u a l r a d i a t i o n r e d u c - present and (ii) photoreduction of at least some of the 6+
t i o n to t r i v a l e n t Cr. F o r t h i s a n d all p r e v i o u s s p e c t r a which is present, though this group's work with transpas-
s h o w n , t a k e off a n g l e s w e r e c h o s e n to e n h a n c e t h e h e x a - sive films on chromium indicates that much of the hexa-
valent species generated may be removed by rinsing be-
v a l e n t r e g i o n in t h e film. C : + is p r e s e n t in t h e t o p s u r f a c e
fore introduction to the spectrometer.
l a y e r s ( a n d t h u s h a s a s t r o n g s i g n a l at low t a k e - o f f angles)
of b o t h e l e c t r o c h e m i c a l l y f o r m e d films a n d t h e t h e r m a l Hexavalent Cr species have been observed most clearly
oxide. I n all cases, v a r i a b l e a n g l e X P S s h o w s t h e tetra- at low p h o t o e l e c t r o n t a k e off angles, a b o u t 10 to 20 ~ ( n o m i -
valent breakdown product forms nearest the surface nal values), in p a s s i v e films f o r m e d o n 304 s t a i n l e s s steel or
w h e r e h e x a v a l e n t Cr is first r e d u c e d a n d o x y g e n c a n b e 19-9 t y p e alloys (2, 3). T h e h i g h v a l e n c e s p e c i e s o p e r a t e in
d e s o r b e d or m o l e c u l a r r e a r r a n g e m e n t c a n o c c u r w i t h t h e u p p e r r e g i o n s of t h e film to e n h a n c e b i p o l a r c a t i o n
g r e a t e s t ease. selectability and improve corrosion resistance. At high
take-off angles the trivalent species usually become domi-
Discussion n a n t a n d t h e h e x a v a l e n t s p e c i e s m o r e difficult to d i s c e r n .
C : +h a s b e e n p r e d i c t e d f r o m t h e r m o d y n a m i c c o n s i d e r a - T h i s is also t r u e of t h e c h r o m a t e d F e s a m p l e s . C h r o m a t e
t i o n s to f o r m d u r i n g t h e o x i d a t i o n o f Cr at e l e v a t e d t e m - h a s b e e n s h o w n (26) to a c t as a n i n h i b i t o r at s u r f a c e cover-
p e r a t u r e s . I n a c a l o r i m e t r i c s t u d y o f t h e h e a t s of o x y g e n a g e s of a b o u t 4%, n e a r t h e l i m i t o f d e t e c t a b i l i t y in X P S .
a d s o r p t i o n o n v a r i o u s m e t a l films, B r e n n a n et aL (24) H e n c e in t h i s case, as i n o t h e r c o r r o s i o n p r o d u c t s y s t e m s
n o t e d t h a t t h e h e a t of o x i d a t i o n of Cr203 to CrO3 is q u i t e for w h i c h t h e Cr s i g n a l is w e a k , r e l a t i v e l y l o n g d a t a acqui-
s i t i o n t i m e s are n e c e s s a r y to p r o v i d e s p e c t r a w i t h h i g h sig-
n a l to n o i s e ratios. L o n g d a t a a c q u i s i t i o n t i m e s will, how-
ever, lead to g r e a t e r p h o t o r e d u c t i o n of t h e h e x a v a l e n t
Table IV. Peak areas from Cr2p3/2 reduction spectra of passivated
species. E x c e s s i v e s m o o t h i n g o f l o w s i g n a l to n o i s e ratio
Fe19Cr9Ni.
s p e c t r a , w h e r e t h e n u m b e r of p o i n t s in t h e s m o o t h i n g in-
t e r v a l e x c e e d s 70% o f t h e full w i d t h of t h e n a r r o w e s t sin-
Peak areas as fraction of multiplet glet p e a k , c a n lead to a loss of f e a t u r e s c o r r e s p o n d i n g to
Species 45 rain 6.5 h s m a l l p e a k s , s u c h as Cr 6~. S p e c t r a f r o m p a s s i v e films m a y
also i n c l u d e d o m i n a n t m e t a l l i c Cr p e a k s w h i c h t e n d to
Cr (metal) 11.8 11.5 m a s k c o n t r i b u t i o n s f r o m b o t h h e x a v a l e n t Cr ( d u e to t h e
CrQ 17.1 23.8 h i g h m e t a l l i c tail) a n d t h e t e t r a v a l e n t d e c o m p o s i t i o n p r o d -
Cr20:~ 49.7 49.5
CrOOH 11.6 11.8 uct. F o r t h i s r e a s o n , t h e c h r o m a t e o n F e is a g o o d e x a m p l e
CrO~} 6.1 2.0 to s t u d y s i n c e n o m e t a l l i c s i n g l e t is i n c l u d e d i n t h e Cr2p.~/z
CrO~ 3.7 1.4 s p e c t r a . X P S a n a l y s i s o f t h e t h e r m a l o x i d e film (Fig. 6) is

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 J. Electrochem. Soc., Vol. 138, No. 10, October 1991 9 The Electrochemical Society, Inc. 2925
Im~mmmm~ml~w
Table V. Peak areas from Cr2p3/2 reduction spectra of
(a) oxidized pure Cr.

Peak areas as fraction of multiplet

Species 5 min 10 rain 45 min

CrQ 15.5 20.0 17.0

Cr2Q 69.0 68.6 71.5
CrOOH 5.2 5.5 6.4

~
CrO3 10.3 6.0 5_2

u n d e r A r to t h e s p e c t r o m e t e r . T h e c h a n g e s i n t h e s p e c t r a
are o b v i o u s as h e x a v a l e n t Cr is r e d u c e d . O n c e a g a i n t h e
a m o u n t o f t e t r a v a ] e n t Cr i n c r e a s e s a n d t h e n d e c r e a s e s
at. slightly after long exposure times, itself partially reducing

i m

(b)

J .

(c)

5a~ 57~ 577 57~ ~73

Binding Energy

Fig. 6. Cr2p3/2 spectra from oxide film formed in situ on pure Cr at

400~ and exposure times of (o) 2 min; (b) 10 rain, and (c) 45 rain.

i
Peak identification: 1, Cr03; 2, CrOOH; 3, Cry03; and 4, Cr02.

also h i n d e r e d b y r e d u c t i o n of t h e CrO3. I n a s e p a r a t e s t u d y
(16) w e h a v e f o u n d r e d u c t i o n b y o n e - h a l f of t h e a m o u n t of
Cr s+ in t h e o x i d e scale d u r i n g t h e first 10 r a i n o f x-ray ex-
p o s u r e . T h e r a t e o f r e d u c t i o n t e n d s to slow a f t e r t h e first
h a l f h o u r for r e a s o n s w e s h a l l e x a m i n e shortly. H e n c e t h e
a c q u i s i t i o n of l o w n o i s e s p e c t r a will r e s u l t i n i n a c c u r a t e
a n a l y s i s of h i g h v a l e n c e Cr s p e c i e s o n t h e surface.
F i g u r e 7a-c s h o w s p h o t o r e d u c t i o n o f a CrO3 p o w d e r 562 580 578 57S 5 7 ~"
s t a n d a r d d u r i n g s e v e r a l h o u r s o f analysis. E v e n t h e 5 r a i n Binding Energy
irradiation spectrum shows significant photoreduction.
R e a c t i o n w i t h w a t e r w a s a p r o b l e m as e v i d e n c e d b y t h e Fig. 7. Cr2p3/2 spectra of Cr03 powder showing photoreduction after
presence of hydrated species in the spectrum, even though irradiation times of (a) 5 min, (b) 20 rain, and (c) 6 h. Peak identifica-
the sample was crushed under Ar and then transferred tion: 1, CrO~-; 2, Cr03; 3, CrOOH; 4, Crz03; and 5, Cr02.
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 2926 J. Electrochem, Soc., Vol. 136, No. 10, October 1991 9 The Electrochemical Society, Inc.

OCrO~ 4m. 3d ~F@

-t l r'mi L,v,i
[] cry% .'1]1~It D
t

lJl
i1 ii l.O//3p 'l z~
N
I0
CFB+ 0 2-

TIME ~ II~!DIRTION (Mln)

CV042" ,...... § H2Q--~CrO(OH ) (C~3§
Fig, B. Cr2p312peak arr from photored-ctionof Cr03 (Fig. 7) as a
percentage of tile total multipletarea. Fig. 9. "Coulombic explosion" mechani~irn for hexavalent photare-
ductian and path of decomposition far CrO~ and Cr02.
to trivaleat products through reaction, with water (trapped
within the powder) and further photoreduction. After 6 h cancy "cascades" (30), which may then result in the
of exposure trivalent Cr becomes dominant. For greater subsequent removal of many bor~dj~g electrons Such a_n
clarity the peak areas are compared in chart format in unstable situation may lead to some degree of atomic rear-
Fig. 8. This is the clearest indication of the reduction oc- rangement [as suggested by the work of Varley (31)] and
curring and the sort of decomposition products which changes in the chemical nature of the c o m p o u n d under
result. study. In maximal valence compounds, such as Cr 6+ which
The reduction of certain high valence oxides has been has no 3d electrons te fill deeper core holes, this effect may
d o c u m e n t e d in the literature from both experimental and lead to changes in the ox_idation state. In C r Q such radia,
theoretical poi.nts of view (27-29). Various e~;perim.enters tio_n damage may proceed more slowly due to the metallic
have shown maximal va!enee oxides such as WO~, Tie2, conductivity of the oxide, allowing electrons other than
and V~O~ to be highly susceptible to reduction during X P S those in the valence band of the oxygen ion to fill the ion-
and Auger analysis (7, 29). Knotek and Feibelman (29) sug- ized core states of chromium.
gest that susceptibility is related to bond ionieity. Those Taking a closer j oak at the energy dependence of x-ray
oxides whose anion-cation components differ in Pauling induced photoreduetion, we note that the cross section for
eleetronegativity by more than 1.7 eV (and hence have a photoelectron emission from the z level (and hence the
strong ionic character in their bonding) were cited as being cross section for damage due to x-irradiation in this model)
particularly vulnerable to reduction. In Tie2 the difference may be given by (32)
is about 2.0 eV. CrOa, therefore, with a difference of 1.9 eV
would be an excellent candidate for reduction. ~z = [(288w e2h)/(3 mc)].
-
rEzs/2/EW23
L B ~ J [2]
The cross section for damage by x-radiation may be
given by (28) where E~, the bindiag energy of the z state, is less than hv
for the incident photon (of energy Ei), For this situation,
Q = a~(C) + b(KVB) + ccr(SE) + d~(brems) [1] therefore, we expect the energy dependence of x-ray in-
duced damage to vary as (El):v/2, becomi!!g less as we ap-
where a, b, c, and d are weighting factors. The first term on proach energies at which the primary x-ray absorption
the right refers to damage resulting from the mechanism mechanism is Compton scattering as opposed to core
o f " c o u l o m b i c explosion." The second refers to damage re- photoemission. We have reeent!y reported on a test of this
sulting from the direct ejection of photoelectrons from the m ech an i sm in which chromated Fe samples were charac-
valence band, and the third refers to damage resulting terized by reflection X A N E S performed at the Cr edge
from the production of secondary electrons in the mate- (5989 eV) at the National Synchrotron Light Source at
rial. Cazaux (28) calculated the damage cross section for Brookhaven National Laboratory (33). In this study it was
valence band effects to be m u c h smaller than that for core found that samples which were analyzed by X PS prior to
photoemission during XPS. Both valence band emission X A N E S showed a distinct reduction in the size of the
and secondary electron effects appear to be of conse- hexavalent pre-edge signal. However, there is further
quence mainly during radiation damage of polymers and proof of the coulombic explosion mechanism of photore-
hydrocarbons, though Madey (27), amongst others, has duetion in this data. The rate of photoreduction would de-
shown that secondary electron emission during Auger pend primarily on three factors: photon flux, damage cross
analysis results in damage to maxima] valence oxides to as section, and n u m b e r of susceptible atoms per unit area.
great or greater a degree than XPS. The final term in Eq. [1] The last factor is the same for both X P S and X A N E S anal-
refers to damage caused by bremmstrahlung radiation, ysis. Since the photon flux was m u c h greater during
which according to a study by Wagner is responsible for X A N E S analysis, one would expect greater reduction;
less than 3% of photoreduction by x-rays in the 1 keV however, both samples were exposed to synchrotron x-
range and above (29). radiation for at least one-half hour prior to analysis (due to
Following the suggestions of Madey and Cazaux (28), we difficulties in alignment, etc.). If reduction were primarily
take the dominant m e c h a n i s m leading to reduction to be flux dependent, no hexavalent pre-edge would be visible.
coulombic explosion (12). In the case of CrOa this mechan- Yet we are using an x-ray energy during X A N E S almost
ism is illustrated in Fig. 9. Here the ejection of a core 4.8 times that of MgKa x-radiation. This makes the damage.
photoelectron from Cr results in an Auger process in the cross section for X A N E S 237 times less than that for MgKa
valence band of 02 in which a temporary positive charge X P S analysis. Hence, in X A N E S studies of the Cr edge at
could be imparted to the oxygen ion. Such an ion may be 5989 eV the reduction of Cr 6+ would be minimal. This
desorbed from the surface or m o v e into a different molecu- helps to explain the ability of synchrotron absorption tech-
lar configuration. The ionization of even deeper core lev- niques to surpass that of X P S in the detection of hexa-
els, using x-radiation of 1 kV, could result in Auger or va- valent species in Cr oxide films (15).

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 J. Electrochem. Soc., Vol. 138, No. 10, October 1991 9 The Electrochemical Society, Inc. 2927

Conclusions 6. J. Detourney, L. DeMiranda, and M. Ghodsi, ibid., 15,

295 (1975).
1. While variable angle XPS is an invaluable tool for 7. S. Storp, Spectrochim. Acta, 40B, 745 (1985).
characterization of surface oxide films, it carries with its 8. R. G. Copperthwaite, Surf. Inter. Anal., 2, 17 (1980).
use the possibility of damage to certain oxide systems 9. T. Sasaki, R. S. Williams, J. S. Wong, and D. A. Shirley,
which meet particular criteria of high valence and chemi- J. Chem. Phys., 68, 2718 (1978).
cal activity. 10. B.A. DeAngelis, J. Electron Spectrosc. Relat. Phenom.,
2. Hexavalent chromium concentrations may be under- 9, 81 (1976).
estimated through XPS analysis of corrosion product lay- 11. A. Cimino, B. A. DeAngelis, A. Luchetti, and G. M i n d -
ers on stainless steel and other systems as a result of the li, J. CataL, 45, 316 (1976).
12. G. P. Halada, C. R. Clayton, and D. H. Lindsley, Mater.
combination of small peak area or low signal to noise ratio
Sci. Eng., Ale3, L5 (1988).
and photoreduction in surface layers by x-rays. 13. G. A. Hope and I. M. Ritchie, Thin Solid Films, 34, 111
3. Products of the reduction of hexavalent chromium (1976).
species include tetravalent CrO2 as an intermediate prod- 14. L. Feve, R. Fontaine, J. Arsene, M. Lenglet, and R.
uct with continued reduction to trivalent states by x-irradi- Caillat, C.R. Acad. Sci. Paris, 301, 701 (1985).
ation or reaction with adsorbed water to form CrOOH. It is 15. G. G. Long, J. Kruger, and D. Tanaka, This Journal,
possible that quantitative analysis of CrO2 may enable an 134, 264 (1987).
estimate to be made of the original Cr 6. content of the film 16. G. Halada and C. R. Clayton, ibid., Submitted.
under analysis. 17. A. Savitsky and M. J. E. Gotay, Anal. Chem., 36, 8
(1964).
4, Photoreduction is heavily dependent on the "damage 18. P. M. A. Sherwood, in "Practical Surface Analysis," D.
cross section" (as defined by Cazaux and further de- Briggs and M. P. Seah, Editors, p. 445, J o h n Wiley &
veloped in this study), which in turn depends upon the Sons, Inc., New York (1983).
energy of the incident photons. This is explained by the 19. D. A. Shirley, Phys. Rev. B, 5, 4709 (1972).
mechanism of "Coulombic explosion" and results in lim- 20. J. R. Scully and D. W. Taylor, in "Metals Handbook,"
ited damage by techniques such as XANES or EXAFS of Vol. 3, "Corrosion," 9th ed., J. R. Davis et al., Edi-
Cr which employ x-rays of energies for which the cross tors, p. 214, Metals Park, OH (1987).
sections of core photoemission is lower. 21. W. Krakow, H. Colijn, and O. Muller, Phil. A, le, 369
(1979).
22. I. Ikemoto, K. Ishii, S. Kinoshita, H. Kuroda, M. A. A.
Acknowledgments Franco, and J. M. Thomas, J. Solid State Chem., 17,
This work was supported by the Office of Naval Re- 425 (1976).
search (Dr. A. J. Sedriks, contract officer) u n d e r contract 23. F. Tsai, Master's Thesis, S.U.N.Y. at Stony Brook
n u m b e r N0001485K0437. (1988).
24. D. Brennan, D. O. Hayward, and B. M. W. Trapnell,
Manuscript submitted Oct. 15, 1990; revised manuscript Proc. R. Soc. London Ser. A, 256, 81 (1960).
received April 26, 1991. This is in part Paper 249 presented 25. A. G. Revesz and J. Kruger, in "Passivity of Metals,"
at the Seattle, WA, Meeting of the Society, Oct. 14-19, 1990. R. P. Frankenthal and J. Kruger, Editors, p. 137, The
The Research Foundation of the State University o f New Electrochemical Society, Corrosion Monograph
York assisted in meeting the publication costs of this ar- Series, Princeton, NJ (1978).
ticle. 26. I. L. Rozenfeld, "Corrosion Inhibitors," McGraw-Hill
Inc., New York (1981).
REFERENCES 27. T. E. Madey, in "Analytical Electron Microscopy--
1. C. R. Clayton, A. R. Brooks, K. Doss, and Y. C. Lu, in 1987," D. C. Joy, Editor, p. 345, San Francisco Press
"Equilibrium Diagrams; Localized Corrosion," R. P. Inc., San Francisco (1987).
Frankenthal and J. Kruger, Editors, PV 84-9, p. 369, 28. J. Cazaux, Appl. Surf. Sci., 20, 457 (1985).
The Electrochemical Society Softbound Proceed- 29. C. D. Wagner, Surf. Inter. Anal., 6, 90 (1984).
ings Series, Pennington, NJ (1984). 30. M. L. Knotek and P. J. Feibelman, Surf. Sci., 90, 78
2. A. R, Brooks, C. R. Clayton, K. Doss, and u C. Lu, This (1979).
Journal, 133, 2459 (1986). 31. J. H. O. Varley, J. Phys. Chem. Solids, 23, 985 (1962).
3. C. R. Clayton and Y. C. Lu, ibid., 133, 2465 (1986). 32. L. C. F e l d m a n and J. W. Mayer, "Fundamentals of Sur-
4. Y. C. Lu, C. R. Clayton, and A. R. Brooks, Corr. Sci., 29, face and Thin Film Analysis," p. 194, North-Holland,
863 (1989). New York (1986).
5. C. R. Clayton and Y. C. Lu, ibid., 29, 881 (1989). 33. G. Halada and C. R. Clayton, To be published.

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