Initial Stages of Oxide Growth and Pore

Initiation in the Porous Anodization of Aluminum

C. J. Dell'Oca *'1 and P. J. Fleming *'1
Fairchild Semiconductor, Mountain View, California 94040

ABSTRACT
Ellipsometry studies of evaporated a l u m i n u m films anodized in 0.6M H~PO4
at constant c u r r e n t indicate that the anodic oxide produced is at first homo-
geneous with a refractive i n d e x of 1.62, as found for b a r r i e r anodic oxide
of t h i n film and bulk A1. As the thickness increases, the optical properties
change signifying the onset of pore formation. This occurs at increasing thick-
nesses with increasing c u r r e n t density, however, pore formation always occurs
well before the peak in voltage is reached at constant current. Ellipsometry
indicates that the mode of d e v e l o p m e n t of the oxide prior to pore initiation
is similar to that of b a r r i e r anodic oxides. However, the efficiency of oxide
growth and the electric field required to pass a given ionic current, J, are gen-
erally lower and approach values for b a r r i e r oxides (of thin film and b u l k
A1) only at high c u r r e n t densities. The c u r v a t u r e of the log J vs. E curve is
in the opposite sense to that n o r m a l l y observed for anodic oxides and it is
i n t e r p r e t e d i n terms of cation and a n i o n motion. After pore formation the
efficiency of oxide growth increases and becomes n e a r u n i t y w h e n steady-state
formation conditions are reached. These results appear consistent with the
model that dissolution at the pore bases is an electric field-aided process.

Anodization of evaporated a l u m i n u m films is be-
coming increasingly i m p o r t a n t in the fabrication of
monolithic, large-scale integrated circuits utilizing alu-
m i n u m metal electrical interconnections where ano-
dization provides both improved processing and re-
liability (1). I n order to arrive at o p t i m u m processing,
it is necessary to u n d e r s t a n d the anodization properties
of a l u m i n u m films. I n a previous paper, the b a r r i e r
anodization properties were studied and found to be
essentially the same as those of b u l k a l u m i n u m (2).
The present study is concerned with porous anodiza-
tion. I n particular, the initial stages of oxide growth
and the onset of pore formation are q u a n t i t a t i v e l y
characterized using ellipsometry. This has not been
done previously for porous anodization of a l u m i n u m
and the results should be valuable i n a r r i v i n g at the
m e c h a n i s m of pore formation.
Of the vast l i t e r a t u r e on porous anodization of alu-
m i n u m , v e r y little deals with initial stages of film
formation. That which does is mostly qualitative be-
cause of the difficulties involved with measuring very
t h i n films. The evidence that is presented indicates
that a b a r r i e r l i k e film initially forms, followed b y
pore initiation and porous oxide growth. For example,
the anodization characteristics, such as the time de-
v e l o p m e n t of c u r r e n t at constant voltage (3) or of
voltage at constant current, are at first similar to
those observed in b a r r i e r anodizations. Also, direct
observations of the surface with electron microscopy
indicate that surface roughness occurs after some
growth has t a k e n place (3, 4). Thus, the oxide formed
i n the initial stages of porous oxide growth and that
which r e m a i n s interposed b e t w e e n the p o r e - c o n t a i n -
ing layer and the metal is often referred to as a b a r -
rier layer. In this paper, these layers will be respec-
tively referred to as the initial film (or oxide) and
the pore-free layer. To avoid ambiguity, the t e r m
"barrier" will be reserved to describe oxides formed
in a b a r r i e r anodization.
The basic difficulty involved with the study of the
initial film is the m e a s u r e m e n t of thickness. Previous
methods include reanodization in b a r r i e r film forming
electrolyte (5) and direct observation of thickness
* Electrochemical Society Active Member.
1Present address: Hewlett-Packard Company, Palo Alto, Cali-
fornia 94304.
Key words: anodization, a l u m i n u m oxide, ellipsometry.
using cross sections and electron microscopy (4). The
first method assumes that the ionic conductivity of
the initial film is the same as that of b a r r i e r oxides.
These methods have limited resolution and accuracy
and, i n addition, are destructive and therefore c u m -
bersome. In the present s t u d y these drawbacks are
overcome using ellipsometry. This is a nondestructive
optical technique that is v e r y sensitive to the pres-
ence of and changes i n thin surface layers. Thus, it
has been widely used to characterize properties of
thin films (6) including those of b a r r i e r oxides formed
on b u l k (7, 8) and thin film a l u m i n u m (2).
If the initial film growth characteristics are as have
been presented, t h e n it should be possible with ellip-
sometry not only to determine the growth properties
but also to determine the onset of pore formation.
That is, the optical properties of the initial film should
at first be similar to those of b a r r i e r oxides which
have been found to be optically homogeneous (2, 7).
The advent of pore formation causes a change of optical
properties which should be detectable b y ellipsometry.
This t u r n s out to be the case.
Experimental
The investigation was carried out with 2 ~m thick
a l u m i n u m films deposited on t h e r m a l l y oxidized pol-
ished silicon wafers by the electron beam evaporation
of 99.999% pure a l u m i n u m u n d e r high vacuum. Films
deposited u n d e r these conditions have b a r r i e r ano-
dization properties which are not detectably different
t h a n those of b u l k a l u m i n u m (2). The t h i n film is
more convenient to use t h a n b u l k a l u m i n u m because
a smooth surface suitable for anodization is obtained
directly without polishing and because photolithog-
r a p h y and etching can be used to precisely define the
anodization area.
Two types of specimens were used and these are
shown schematically in Fig. 1. One type had a 3.22
cm 2 anodization area defined using photolithography
and etching of a previously formed, 2700A thick, b a r -
rier anodic oxide on the a l u m i n u m film. The other
type bad a circular 10 cm 2 a l u m i n u m area defined b y
photolithography and etching of the deposited alu-
m i n u m film. A n a l u m i n u m strip 1 mil wide was left
to connect the a l u m i n u m in the contact area to the
anodization area. The strip is of negligible area b u t

1487
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 1488 J. Electroche~. Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y October 1976
28C
..Contact 1400

/ / ~lmil ~. " ~ /
24C 1800"-/

-"Anodization-~
~ ~ / ~lOcmz ; / zooe2
20C V _
Area AIzO3 n.= 1.62+ o.o2 "}100

Fig. 1. Schematic representation of the two types of thin film A/deg AI, n =I.3+0.I
aluminum specimens used in this study. k = 6.5+ 0.3
220C
it is sufficiently long to keep the contact area above 16C
the electrolyte d u r i n g anodization. The first type of
specimen was used mostly for kinetic studies while ) I000~
the second type was used for density m e a s u r e m e n t .
No noticeable difference i n oxide growth was noted
b e t w e e n these two surface p r e p a r a t i o n methods.
The anodizations were carried out at c o n s t a n t c u r -
12C
r e n t (regulated to 0.3%) i n a stirred 0.6M H~PO4 i
200
electrolyte held at 25~ +_ 0.2~ This electrolyte was
chosen because the pore-free portion of the porous
oxide can, depending on c u r r e n t density, be varied
over a substantial thickness range, leading to a more
precise d e t e r m i n a t i o n of film properties. The anodiza- v i
tions were carried out in a stepwise fashion with el- 80 410 4r5 50 5~5
lipsometry m e a s u r e m e n t s made on the surface prior ~/deq
to anodization and after each anodization step. All
ellipsometry m e a s u r e m e n t s were made at 70 ~ angle Fig. 2. EIlipsometry results and fitted curve for anodizatlon of
of incidence using a He-Ne laser unpolarized light aluminum films in 3% tartaric acid (pH of 5.5) at 25~ (2).
source of 6328A wavelength. Other e x p e r i m e n t a l de- Numbers along curve indicate film thickness.
tails are as described i n a previous paper (2).
270 1 5 m A cm -~
Results
Optical properties.--Since the analysis of ellipsom- ~.1300
etry results from the initial film relies heavily on the ,,,',. / - 10 r n A c m - ~
etlipsometry characteristics of b a r r i e r anodic oxide
formed on evaporated a l u m i n u m films, the latter re-
sults are quoted in Fig. 2 (2). This figure presents the
conventional ,~ vs. ~ plot used in ellipsometry, where / , 5mAcrn-~
A and ~ are the quantities d e t e r m i n e d in ellipsometry
and are related to the properties of the film and u n d e r -
lying substrate. The e x p e r i m e n t a l results begin at
210 I/ 2mAcro-21; \A
kk~
the point m a r k e d "bare" substrate which represents
the surface of the a l u m i n u m film prior to b a r r i e r I
I 1100
anodization in a tartrate solution. As the surface is
anodized and remeasured at intervals, the experi-
m e n t a l points obtained (denoted b y crosses) trace
I
A F2200 , ~
out, i n a counterclockwise direction, a n elliptically
shaped curve which e v e n t u a l l y recycles on itself as deg I l
indicated b y the circular points. The curve i n the
figure represents the best fit to the e x p e r i m e n t a l points
indicating a u n i f o r m oxide with an index of refrac-
150
~/0.0~ -I,000
tion (N ---- n -- jk) of 1.62 on a l u m i n u m having a
~ .,,_._ U n a n o d i z e d /~_
refractive i n d e x of 1.3-6.5.
Surface / n =1.62
As expected, the ellipsometry results characteristic
v /
of initial film growth i n 0.6M H3PO4 are at first
similar to those of b a r r i e r oxides. Figure 3 shows a \ /
superposition of results from various anodization cur-
r e n t densities. The dashed curve i n this figure is the
Y~300 / 7900
ellipsometry curve for b a r r i e r anodization taken from
Fig. 2 and it serves as a reference. The ellipsometry
m e a s u r e m e n t s t a k e n at interva]s d u r i n g porous ano-
90
dization at first are coincident with the reference 6OO
curve indicating that the initial film has the optical I I I I I I
properties of b a r r i e r films. For sake of clarity, the 40 45 50
e x p e r i m e n t a l points are not shown. Eventually, the /deg
e x p e r i m e n t a l curve deviates from the reference curve
signifying a change in optical properties, i.e., the pres- Fig. 3. Departure from dashed curve representing the homo-
ence of pores. The reproducibility of these results is geneous film in Fig. 2 of ellipsometry results from oxides formed at
good in the region before deviation and for some time various current densities on AI in 0.6M H3PO4.
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 VoI. 123, No. 10 POROUS ANODIZATION OF ALUMINUM 1489

after deviation from the reference curve. The repro- 29C

ducibility becomes less good at large deviations, i.e.,
n e a r the ends of the e x p e r i m e n t a l curves.
270
A q u a n t i t a t i v e analysis of these results is not feasible
because of the complex mode of film growth after
pore initiation. That is, the growth rates of the i n - 250 ..... (_/_
itial and pore containing layers are expected to, re-
spectively, decrease and increase in a complex way.
I n addition, the size and n u m b e r of pores is expected 230
o..,.,,, ,.0~176
to change with voltage u n t i l the steady-state voltage 6~ 120o
is reached in the constant c u r r e n t anodization (4).
210
A f u r t h e r complication to this picture is that i n 1400 ~Xx~x IIOO)
addition to pore formation at the upper surface of
the growing film, after a while, r o u g h e n i n g of the 190
a l u m i n u m also occurs, effectively changing its optical
A
properties. deg
A qualitative analysis of the e x p e r i m e n t a l results 170
is instructive and can be made using a simplified model
of growth. I n this model it is assumed that, once the
150 AI /Ooool
pores begin to form, these pores have a fixed size
and they penetrate the growing layer at some fixed / ~ o.o A /
rate. Indicative calculated ellipsometry curves are 130 I /
given i n Fig. 4 and 5. The respective thicknesses at
which pore formation begins are chosen as 500A (Fig. ~\ ,//
\ it
4) and 1000A (Fig. 5) to, respectively, correspond to 110
\ iI
the 2 and 5 m A / c m 2 formation currents. \\ II
The simplest case is one where the pores grow at \\ //
90 -- \x //
a rate equal to film growth. I n other words, the initial
l a y e r r e m a i n s fixed at the p o r e - i n i t i a t i o n thickness.
Optically, this corresponds to a porous layer growing
40 45 50 55
over a pore-free l a y e r of fixed thickness and refrac-
",I/
290 deg
Fig. 5. Same as in Fig. 4 but for the case of pore initiation at
1000/~, and layer 2 fixed at 1000~, ( - - A - - A = 5 mA/cm ~- experi-
27"0
mental points from Fig 3).

250 tive i n d e x of 1.62. This simple model predicts that

the refractive index of the porous layer must be lower
t h a n that of the b a r r i e r films i n order to obtain ellip-
230 [d-5oo) s o m e t r y curves that deviate on the correct side of
reference curve (Fig. 4 and 5). This behavior is
/ expected since the presence of pores decreases the
210 density of the oxide.
// A pore growth rate less t h a n that of film growth, i.e.,
tI an initial layer that continues to grow at some rate
190 -- after pore initiation, has the effect of moving the
/x, calculated curves i n Fig. 4 and 5 closer to the ref-
deg erence curve. I n the extreme case where only the
17'0 -- initial layer grows (i.e., no pore formation), the ref-
erence curve is regained. A calculated curve which
comes close to the 2 m A / c m 2 results is shown in Fig.
150 -- 4. I n this case, after pore initiation at 500A, a porous
layer of refractive index 1.3 contributes 80% of the
total increase in film thickness.
150 -- One characteristic difference b e t w e e n the calcu-
lated and e x p e r i m e n t a l curves is that with increas-
ing thickness the former t u r n and proceed to pass
II0 -- n e a r the point m a r k e d 0.0A, which represents the
original surface. The e x p e r i m e n t a l results do not have
this t e n d e n c y because as the pores grow, a scallop is
developed i n the a l u m i n u m surface u n d e r each pore
cell (4). The result is a fine grain surface roughness
(600) which effectively changes the refractive index of the
t 1 , .L
70 F , ~ ~ [ , , q I ~ , u
a l u m i n u m and shifts the ellipsometry results.
40 45 50 55
Pore initiation.--As a first approximation, the onset
of pore formation is d e t e r m i n e d from the point where
deg the ellipsometry curve begins to deviate from the
Fig. 4. Calculated ellipsometry curves using a two-layer approxi- reference curve (Fig. 3). This point occurs approx-
mation of film growth after pore initiation occurs at 500~,. i m a t e l y at 600, 1050, 1150, and 1275A, respectively, for
Layer 2 fixed at 500A; . . . . layer 2 contributes 20% of the formation currents of 2, 5, 10, and 15 m A / c m 2. The
total film growth; - - - - - - reference curve from Fig. 1; O O O accuracy w i t h i n which these points can be d e t e r m i n e d
= 2 mA/cm 2 experimental points from Fig. 3; numbers indicate depends on where the deviation occurs on the ref-
total film thickness, d, and bracketed numbers apply to reference erence curve. The sensitivity is higher in the 900-
curve, 1200A region t h a n at the apex of the reference curve.
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 1490 J. E l e c t r o c h e m . Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y O c t o b e r 1976

T h e voltage of pore initiation is d e t e r m i n e d from

the above thickness using a g r a p h of voltage vs.
thickness for the various anodization c u r r e n t densities.
!2S, Aom-, /'
(This figure is p r e s e n t e d l a t e r in the section on g r o w t h
properties.) The i m p o r t a n t result h e r e is that p o r e
initiation occurs well before the p e a k in voltage is
reached in the constant c u r r e n t anodizations. F i g u r e
6 shows the v o l t a g e - t i m e curves which are c h a r a c -
teristic of porous a l u m i n u m anodization and typical
for the p r e s e n t experiments. The onset of p o r e f o r m a -
tion occurs at about 70% of the s t e a d y - s t a t e voltage.
,;///
~
O ' S u l l i v a n and Wood using electron microscopy have
r e p o r t e d for anodizations at 5 m A / c m 2 in 0.4M H3PO4
at 25~ that v e r y m i n o r film roughening is noted after I
40 sec of g r o w t h (4). This is in a g r e e m e n t w i t h the
p r e s e n t results at the same c u r r e n t d e n s i t y in a some-
w h a t m o r e concentrated electrolyte.
The thickness at which the onset of pore f o r m a t i o n
occurs has p r o b a b l y been o v e r e s t i m a t e d to some d e -
gree. This is because the d e v i a t i o n from the reference o'- ' 4~ ' do ' 1~o ' 1;o
TIME (secl
curve occurs slowly with changing film thickness.
Some indications of how slowly can be obtained from Fig. 7. Typical initial film thickness development with time for
the calculated curves of Fig. 4 and 5. If a s i m i l a r various anodization current densities.
estimation of pore initiation is m a d e for these curves,
then the onset of p o r e f o r m a t i o n would be thought to 120
occur at about 600A (Fig. 4) and 1050A (Fig. 5) when,
in actuality, it began at 500 and 1000A, respectively.
However, it is h i g h l y u n l i k e l y that pores are p r e s -
ent and g r o w from the outset of the anodization. This
would r e q u i r e the p o r e - c o n t a i n i n g p o r t i o n of the film
to r e m a i n r e l a t i v e l y insignificant until n e a r the point
of deviation and then almost a b r u p t l y become sig-
nificant. To be insignificant, the p o r e - c o n t a i n i n g l a y e r
should change the r e f r a c t i v e i n d e x of the o v e r - a l l
film b y less than 1% for the formations above 2 m A /
cm 2. I n addition to this argument, the thickness d e -
t e r m i n e d b y e l l i p s o m e t r y was checked at various
"~lOmAcm- 2
points along the 10 m A / c m 2 anodization b y an i n d e -
p e n d e n t m e t h o d utilizing the Tolansky i n t e r f e r e n c e
m e a s u r e m e n t of the height of a silvered step formed 40 ~ m A c m _ 2
in the anodic oxide. These m e a s u r e m e n t s w e r e found
to be in agreement.
Characteristics of initial film g r o w t h . - - T h e charac-
teristics of initial film g r o w t h at constant c u r r e n t in
I r I I I I I I I I I I I
0.6M HsPO4 at 25~ w e r e found to be s i m i l a r to those
0 5 10
of b a r r i e r oxide growth. That is, the thickness in-
THICKNESS xlO -2 (/~)
creases l i n e a r l y with t i m e and the voltage increases
l i n e a r l y with thickness. Typical results are given in Fig. 8. Typical cell voltage development with initial film thick-
Fig. 7 and 8. The thickness was d e t e r m i n e d using ness for various anodization current densities.
e l l i p s o m e t r y and the optical p r o p e r t i e s of b a r r i e r
film (reference curve of Fig. 3). In some cases the a l r e a d y mentioned. These results w e r e g e n e r a l l y quite
thickness was checked b y the i n d e p e n d e n t m e t h o d reproducible.
The efficiency of oxide growth, i.e., oxygen uptake,
and the efficiency of a l u m i n u m consumed d u r i n g the
anodization w e r e d e t e r m i n e d and found to be differ-
ent. The efficiency of oxide g r o w t h is low and increases
lOmAcm-2
with c u r r e n t d e n s i t y of f o r m a t i o n (Table I). The
efficiency is calculated using F a r a d a y ' s l a w for an
oxide of f o r m u l a A120~, and the rate of film g r o w t h
5m,&cm-2 d e t e r m i n e d f r o m the e x p e r i m e n t a l thickness vs. time
curves. A n oxide density of 3 g / c m 3 was used in
these calculations. This is within the r a n g e of values
(2.90-3.2 g/cm3) obtained from our m e a s u r e m e n t s of
d e n s i t y and is a value that has been used b y others
(9). By comparison, b a r r i e r films f o r m e d in a t a r t r a t e
2mAcm-2
Table I. Efficiency of initial oxide growth in 0.6M H~P04 at 25~

Applied Electric Growth Growth

current field rate efficiency
( m A / c m 2) ( l0 s V / c m ) (A/sec) (%)
, ~ r
TIME (re,n) 2 5.5 fi 43
5 6.74 14 47
Fig. 6. Time development of voltage far porous anodization at 10 7.66 30 51
15 8.2 51 58
various current densities showing the onset of pore formation, 25 8.6 109 74

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 Vol. 123, No. 10
solution at the same temperature, have efficiencies
close to 70 and 80%, respectively, at 2 and 10 m A / c m 2
formation (2). While the efficiency of oxide formation
is low, the efficiency of a l u m i n u m used in the anodiza-
tion approaches unity. This was d e t e r m i n e d from cal-
culations based on the difference in weight from prior
to anodization to after anodization and removal of
the anodic oxide. That is, the a m o u n t of a l u m i n u m
used in the anodization corresponds to that predicted
from Faraday's law for the charge passed. This i n -
dicates that, w i t h i n e x p e r i m e n t a l error, electronic
currents are not c o n t r i b u t i n g to c u r r e n t transport
through the oxide. Hence, the low efficiencies ob-
served for oxide growth occur from the loss of alu-
m i n u m to the electrolyte b y oxide dissolution.
The open-circuit oxide dissolution rate i n the elec-
trolyte was m e a s u r e d and found to be less t h a n 0.2A/
sec which is insignificant w h e n compared to the rates
of oxide growth. The effect was f u r t h e r minimized
b y m i n i m i z i n g the open-circuit exposure of oxide to
the electrolyte. Thus, oxide dissolution must be a
function of electric field i n the oxide in order to cause
the observed loss i n oxide growth efficiency. This
is discussed later.
The growth kinetics of the initial oxide, i.e., the
log of ionic c u r r e n t density vs. electric field, are given
i n Fig. 9. The electric field is obtained from the slope
of the voltage vs. thickness curves. The ionic c u r r e n t
density (dashed curve, Fig. 9) is the applied c u r r e n t
d e n s i t y (left curve, Fig. 9) corrected for efficiency of
growth. The curve on the right i n Fig. 9 represents
the growth kinetics for b a r r i e r oxide formed in a
t a r t r a t e solution. It is seen that at high c u r r e n t densi-
ties the growth kinetics of the initial oxide approach
that of b a r r i e r oxides. At lower currents, the ionic
conductivity of the initial film is significantly higher
t h a n that of b a r r i e r oxides. Also, note that the electric
fields are lower t h a n the 107 V / c m which have b e e n
reported to occur across the dense oxide after steady-
50
i I I i
0.7 M HsPO4
I Applied Current Density
- - - Ionic Current Density
<[ .; ~j//l'~//
E /'
- /
/
/ field F r e n k e l defect theory of ionic conduction in anodic
/ oxides and the mobility of both oxygen (anions) and
/
/ metal (cations) ions d u r i n g oxide growth. There is
/
/ a n d m e t a l - o x i d e interface, respectively. [For a r e -
i //
/
/
I'
- /
5 7 8 9
E x10-6 (V/cm)
Fig. 9. Constant current kinetics of initial film growth in 0.CM
"H3PO4 at 25~ Curve to the left represents applied current
density. Dashed curve is the ionic current density. The curve on
t~e right gives the kinetics obtained in the barrier anodization of
AI films (2).
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POROUS ANODIZATION OF A L U M I N U M 1491
state porous oxide growth is reached in the same
electrolyte (4).
The higher ionic conductivity of the initial film
does not appear to be an artifact of the thickness
measurements. Systematic m e a s u r e m e n t errors in
thickness do not en.ter because rates of change rather
t h a n absolute values are used to d e t e r m i n e growth
efficiency and electric field. I n order to observe a
lower field, the initial film thickness must be over-
estimated by a factor that increases with thickness.
This is highly u n l i k e l y even if it is assumed that
pore formation occurs far earlier t h a n estimated. If
pore formation occurred m u c h earlier t h a n has been
estimated, then it might be expected that the effective
film thickness for ionic conduction would be less,
hence reducing the r e q u i r e d voltage and leading to a
lower estimate of electric field. C o n t r a r y to this is
the fact that the presence of pores effectively decreases
the anodization area and hence increases the effective
c u r r e n t density and, i n t u r n , the electric field. Thus,
the measured electric field across the pore-free layer
is far greater t h a n that of the b a r r i e r films, being
on the order 10T V / c m (4). I n addition, if pores are
present, the qualitative indications (Fig. 4 and 5) are
that using the reference curve, ellipsometry would
u n d e r e s t i m a t e the thickness of the film and hence the
efficiency of oxide growth would also be u n d e r e s t i -
mated. This would have the effect of b r i n g i n g the ionic
c u r r e n t (Fig. 9) closer to the applied c u r r e n t and
hence lowering the electric field. Thus, it is not clear
that early pore formation would lead to an u n d e r -
estimation of the electric field. I n any event, the pres-
ent evidence and that from direct observation (4)
almost exclude early pore formation.
Steady-state porous oxide g r o w t h . - - A l t h o u g h it is
not the i n t e n t i o n of this paper to characterize porous
film growth, it was found that the growth rate is
significantly higher d u r i n g steady-state porous ano-
dization. That is, after the voltage reaches a more or
less constant value u n d e r constant applied current.
A typical result for the 10 m A / c m 2 anodization is
shown i n Fig. 10. The thickness of the initial film
was d e t e r m i n e d by ellipsometry and b y Tolansky
interference m e a s u r e m e n t of step height. The thickness
of the porous film was d e t e r m i n e d solely by the latter
method and also b y a mechanical surface profilometer.
The results extend out to film thicknesses beyond 3 #m.
Discussion
Kinetics of oxide g r o w t h . - - T h e optical properties of
the initial oxide formed in a porous anodization of
a l u m i n u m are similar to those of the b a r r i e r anodic
oxides. The log J vs. E characteristics do appear to be
/ different, b u t this does not necessarily i m p l y a differ-
ent mechanism of ionic conduction. I n fact, it m a y be
argued that these results are consistent with the high
a body of evidence indicating that both ions are mobile
and contribute to oxide growth at the oxide-electrolyte
view of anodic oxides see Ref. (11) and (12).] Ac-
cording to the F r e n k e l defect theory (10), ionic con-
duction occurs b y a t h e r m a l l y activated electric field-
i
aided process i n which ions of charge q overcome
energy barriers of height W and have a h a l f - j u m p
(activation) distance of a. The ionic c u r r e n t density
then is J = A e -(W-qaE)/~T, with A, W, and qa charac-
teristic of the particular ion species. I n a log J vs. E
plot, each ion c u r r e n t will be represented by a straight
line of slope proportional to the product qa. The two
lines will intersect at some point. The total c u r r e n t
(sum of the ion currents) will be dominated b y the
ion with the lower qa below this point and b y the
ion with the higher qa above this point. Thus, the
 1492 J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y October 1976

incorporation will become more noticeable at higher

I.I - currents. In fact, if i m p u r i t y incorporation occurs with
A1208, it should be expected that at higher currents
t h a n those used in this study the log J vs. E curve
1.0
for the initial oxide would tend to curve back in the
direction found for oxides of Ta, AI, and Nb.
0.9
Thus it appears that the kinetics of initial film
growth can be analyzed in terms of anion a n d cation
currents. Then, in the linear region, i.e., at low cur-
0.8 rents, the activation or h a l f - j u m p distance should be
calculated for an a n i o n with a valence charge of q =
0.7 ~ PorousFilm --2e for O - - or q = --e for O H - as proposed b y Hoar
and Mo~t (16). The activation distance found is 1.1

v
:L 0.6
and 2.2A, respectively, which are not unrealistic val-
ues. A n activation distance for cation motion cannot
be obtained because the present data do not reach
bJ
Z
high enough c u r r e n t s where p r e s u m a b l y the l i n e a r
x--
0.5 / region for c a t i o n - d o m i n a t e d conduction is found. How-
o
I I ever, there seems to be a t e n d e n c y toward a line sim-
F- I ilar to that of the b a r r i e r oxide kinetics. Based on
0.4 I
I a metal ion with q of 3e, a n activation distance close
I to 3A is obtained both for b a r r i e r oxides formed on
I thin film (2) a n d b u l k a l u m i n u m (9).
0.3 I
I
I Pore formation.--The two observations i m p o r t a n t
0.2
I to pore formation and growth are the efficiency of
I initial film formation and its increase d u r i n g porous
I
film growth. Both of these observations are in direct
0.I ,~Inttial Film support of the model that etching at the pore bases
is an electric field-aided process (16). First, although
I I
the efficiency of initial film growth increases with
0
50 100 15O 200 c u r r e n t density (and hence electric field), the net
TIME(sec) dissolution rate (inefficiency) also increases with cur-
r e n t density or electric field. I n fact, the rate of dis-
Fig. 10. Development of film thickness with time for a 10 mA/ solution increases e x p o n e n t i a l l y with electric field,
cm2 porous anodization in 0.6M H3P04 at 25~ except at the higher c u r r e n t density where the rate
of increase is slower. Secondly, as the porous film
total c u r r e n t will have a curve whose slope increases grows, the electric field across the porous oxide be-
with electric field as is observed in this study. comes m u c h less than across the pore-free layer;
The foregoing a r g u m e n t was first presented (11) therefore, the efficiency of growth should become near
to show the inconsistency of the F r e n k e l defect theory u n i t y since the su/~face dissolution is decreasing.
and the c u r v a t u r e observed for anodic oxides of Ta, I n addition to field-assisted dissolution, it is also
A1, and Nb. The c u r v a t u r e for these oxides is in the claimed that some anion motion is necessary to sus-
opposite sense, i.e., the log J vs. E curve slowly de- tain porous film growth (16). Dissolution requires
creases in slope with increasing electric field, giving high fields. Fields corresponding to 107 V / c m have
a log J cc aE -- pE 2. While n u m e r o u s models have been observed across the pore-free layer for anodiza-
been proposed [see Ref. (11) and (12)], it is not tion in dilute H3PO4 (4). However, from the observa-
k n o w n whether the effect is intrinsic to ionic con- tion of initial film growth, a n i o n - c u r r e n t dominance
duction or whether, as has been proposed (13), caused occurs at lower fields. There are several explanations
by incorporation of electrolyte impurities into the for this a p p a r e n t inconsistency. One is that oxide
oxide. It has been found that the c u r v a t u r e is enhanced c u r v a t u r e tends to increase the electric field at the
for Ta anodized in dilute H3PO4 or more concen- surface of the pore base while the b u l k of the pore-
trated H2SO4, where i m p u r i t y incorporation is more free oxide experiences lower fields. However, i n order
p r o n o u n c e d (12). to explain this in terms of anion and cation electric
If impurities cause curvature, w h y is the c u r v a t u r e field dependent currents, it is necessary to postulate
not noted for the present anodization in H3PO4? P e r - the buildup of space charge in the oxide. A more
haps i m p u r i t y incorporation is much smaller in Al20.~. likely explanation appears to be that of fringing
Or, the effect m a y simply be overwhelmed by the electric fields. That is, ionic conduction takes place
change from oxygen to metal ion c u r r e n t domination. not only as postulated through the oxide s u r r o u n d i n g
However, it is certain that the low efficiencies, p a r - the pore base (4) b u t also for some distance up the
ticularly at low currents, serve to minimize the frac- pore wall. The idea is not unreasonable, w h e n it is
tion of o x i d e - c o n t a i n i n g impurities. If the incorporated considered that ionic conduction t h r o u g h the initial
impurities are, as has been indicated (14), immobile film is observed to occur at fields that are considerably
with respect to the rate of oxide growth, then incor- lower t h a n that effectively across the pore base oxide.
poration of the impurities into the oxide will only Thus, ionic conduction can occur to (or from) points
occur if the m e t a l ion transport n u m b e r , ~m,2 is greater on the pore wall surface which are separated from
t h a n the difference b e t w e e n the efficiency of oxide the metal by distances considerably larger than the
growth and unity. The tm for A1 anodization in H3PO4 thickness of the oxide under the pore base. Proceeding
is not known. However, it is expected to increase from the pore base up the pore wall, the electric field
with c u r r e n t density of formation. For example, for will decrease in some fashion. The decreasing field is
the anodization of A1 in another aqueous electrolyte accompanied by decreasing ionic current which, in
( a m m o n i u m citrate), tm varied from 0.56 at 1 m A / c m 2 turn, has an increasing oxygen ion component. Since
to 0.72 at 10 m A / c m 2 (15). Since both the efficiency this current flow is toward the metal under the pore
and tm increase with c u r r e n t density, the effect of wall, this is exactly what is necessary to build up
the pore wall. I n addition, since the fringing fields
*~tm is t h e f r a c t i o n of o x i d e w h i c h g r o w s at t h e o x i d e - e l e c t r o l y t e also support dissolution, a v a r i e t y of pore shapes n e a r
interface f r o m m e t a l ion t r a n s p o r t . T h e r e m a i n i n g oxide g r o w s at
the metal-oxide interface f r o m o x y g e n i n transport. the pore base are possible depending on w h e t h e r the

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 VoI. 123, No. 10 POROUS ANODIZATION OF ALUMINUM 1493

fringing field causes net growth or dissolution at a
point.
T u r n i n g to the m e c h a n i s m of pore initiation, it is
difficult to reconcile the present ideas of field-aided
ionic conduction and oxide dissolution with an oxide
thickness i n s t a b i l i t y resulting in a pore. What is even
more perplexing is that at a given c u r r e n t density
pore initiation occurs after a certain oxide thickness
is reached. Perhaps, at a given c u r r e n t density, a cer-
tain thickness must be reached before the allowed
local variation in oxide thickness reaches a value
where the probability of pore initiation is high. Pore
initiation might occur at the edge of such a region
where the gradient in electric field gives rise to a
v a r y i n g i n t e r p l a y of dissolution, oxide growth, and
perhaps metal and oxygen ion motion.
Conclusions
Ellipsometry has been shown to be a useful tech-
n i q u e for s t u d y i n g initial film growth i n porous alu-
m i n u m anodization. It can be used to d e t e r m i n e both
the growth properties and the onset of pore formation.
The initial films formed i n the course of porous a n o -
dization resemble o r d i n a r y b a r r i e r films both optically
and in their mode of development. However, the elec-
tric field required to grow these films is significantly
lower and approaches values for o r d i n a r y b a r r i e r films
only at high c u r r e n t densities.
The observations that film dissolution increases with
field, that the efficiency of oxide growth increases
after pore initiation, and that the fields causing growth
are significantly smaller prior to pore formation ap-
pear to be i n direct support of the model presented
b y Hoar and Mort (16), that the dissolution at the
pore base is a field-aided process.
Manuscript submitted Jan. 13, 1976; revised m a n u -
script received J u n e 18, 1976.
A n y discussion of this paper will appear in a Dis-
cussion Section to be published in the J u n e 1977
JOURNAL. All discussions for the J u n e 1977 Discussion
Section should be submitted b y Feb. 1, 1977.
REFERENCES
1. See Ref. 1-5 of C. J. Dell'Oca, Thin Solid Films, 26,
371 (1975).
2. C. J. Dell'Oca, ibid.
3. T. P. Hoar and J. Yahalom, This Journal, 110, 614
(1963).
4. J. P. O ' S u l l i v a n a n d G. C. Wood, Proc. R. Soc.
London, Sec. A, 317, 511 (1970).
5. M. S. H u n t e r and P. Fowle, This Journal, 101,
481 (1954).
6. See, for example, E. Passaglia R. R. Stromberg,
and J. Kruger, Editors, "Ellipsometry i n the
Measurement of Surfaces and Thin Films," NBS
Misc. Pub. 256, Washington, D.C. (1963).
7. R. M. Goldstein, R. J. Lederich, and F. W. L e o n -
hard, This Journal, 117, 503 (1970).
8. M. A. Barret and A. B. Winterbottom, i n "First
I n t e r n a t i o n a l Congress on Metallic Corrosion,"
p. 657, Butterworths, London (1961).
9. A. C. Harkness and L. Young, Can. J. Chem., 44,
2409 (1966).
10. L. Young, "Anodic Oxide Films," Academic Press,
New York (1961).
11. W. S. Goruk, L. Young, and F. G. R. ZobeI, in
"Modern Aspects of Electrochemistry," Vol. 4,
p. 176, P l e n u m Press, New York (1966).
12. C. J. Dell'Oca, D. L. Pulfrey, and L. Young, in
"Physics of T h i n Films," Vol. 6, p. 1, Academic
Press, New York (1971).
13. C. J. Dell'Oca a n d L. Young, This Journal, 117,
1548 (1970).
14. J. J. Randall, W. J. Bernard, and R. R. Wilkinson,
Electrochim. Acta, 10, 183 (1965).
15. J. A. Davies, B. Domeij, J. P. S. Pringle, and
F. Brown This Journal, 112, 675 (1965).
16. T. P. Hoar and N. F. Mott, J. Phys. Chem. Solids,
9, 97 (1959).

Line Emission Penetration Phosphors: Preparation

and Cathodoluminescent Properties
S. Ignasiak *,1 and H. Veron 2
Sperry Research Center, Sudbury, Massachusetts 01776

ABSTRACT
The p r e p a r a t i o n of three rare earth phosphors with onionskin b a r r i e r
layers is described. The n e w materials are l a n t h a n u m oxysulfides and oxy-
sulfates activated with t e r b i u m and in some cases coactivated with europium.
When these phosphors with high dead voltage, and green emission are mixed
with a commercial phosphor, such as YVO4: Eu, a p e n e t r a t i o n phosphor results
which has four distinct colors as a function of voltage i n CRT displays. The
emission from this phosphor system is at all times n a r r o w band.

Several methods have been developed which allow
the generation of multicolor displays on c a t h o d e - r a y
tubes (CRT). W h e n the color is d e t e r m i n e d by the
accelerating potential on the electrons from a single
electron gun, these devices often use several phosphor
layers either as discrete layers on the face of the CRT
(1-3) or as layered "onionskin" particles (4). A m o n g
the latter group a practical phosphor m i x t u r e has
been developed using a sulfide phosphor with green
emission and an i n e r t onionskin coating or containing
* Electrochemical Society Active Member.
1 P r e s e n t a d d r e s s : C o u l t e r Information Systems, Incorporated,
Bedford, Massachusetts 01730.
2 p r e s e n t address: Mitre Corporation, Bedford, Massachusetts
01730.
K e y words: l a n t h a n u m oxysulfide, l a n t h a n u m oxysulfate, barrier
layer phosphors, europium, terbium.
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a phosphor poison (5, 6). This coated phosphor is mixed
with a commercial r e d - e m i t U n g phosphor. W h e n the
m i x t u r e is excited b y a n electron beam, the red emis-
sion is visible at low energies, b u t as the energy of the
electrons is increased, the b a r r i e r of the coated phos-
phor is penetrated and green light is emitted. The grad-
ual increase i n green emission with increasing beam
voltage creates orange, yellow, a n d finally green light.
This particular system has a broad w a v e l e n g t h emis-
sion in the green portion of the visible spectrum a s
opposed to the line emission typical of rare earth ions.
Three n e w onionskin phosphors have b e e n developed.
They have a b a r r i e r layer and they emit intense n a r r o w
w a v e l e n g t h green light only at sufficiently high a c -
celerating voltages. These rare earth b a r r i e r phosphors