On the Growth of Highly Ordered Pores in Anodized

AluminumOxide
Fei yue Li ,

Lan Zhang,

and Robert M. Metzger*

Center for Materials for I nformation Technology and Department of Chemistry, Box 870336,
TheUniversity of Alabama, Tuscaloosa, Alabama 35487-0336
Received March 17, 1998. Revised Manuscript Received May 21, 1998
I t i s now establ i shed that hexagonal l y ordered domai n structures can be formed i n anodi c
al umi na fi l ms by repeated anodi zati on and stri ppi ng of the porous oxi de. We fi nd that the
domai n si ze i s a l i near functi on of ti me and i ncreases wi th temperature. The pore densi ty
i s i ni ti al l y hi gh but decreases wi th anodi zi ng ti me, as domi nant pores deepen. Very smal l
pores exi st i n nati ve oxi de i n ai r or nucl eate after el ectropol i shi ng. Pore growth may start
when the el ectri c fi el d i ncreases at the pore bottoms, and aci d di ssol ves the oxi de l ocal l y.
1. Introduction
The protecti on or decorati on of Al surfaces by anod-
i zati on has been used commerci al l y si nce at l east 1923.
1
Sel f-organi zed nanopore structures i n anodi c al umi na
fi l ms, cal l ed al umi te, have attracted great attenti on
2-8
due to thei r hi gh pore densi ty and thei r potenti al use
for maski ng or i nformati on storage.
5,9
When the pores
are fi l l ed wi th metal s or semi conductors i n a subsequent
al ternati ng-current reducti ve el ectrol ysi s, these fi l ms
can be fabri cated i nto i nteresti ng magneti c recordi ng,
el ectroni c, and el ectroopti cal devi ces.
5,7,11-22
These
nanopores can be used as templ ates for formi ng arrays
of nanowi res ei ther embedded i n al umi te
9,11,12,14,16-21
or
freed by a subsequent chemi cal removal of the al umi te
structure.
7,23,24
Two forms of anodi c al umi num oxi de exi st, the
nonporous barri er oxi de and the porous oxi de. When
Al i s anodi zed i n neutral or basi c sol uti ons (pH > 5), a
fl at, nonporous, featurel ess i nsul ati ng barri er oxi de
forms,
8
the barri er-type fi l m (BTF). When Al i s
anodi zed i n an aci d [usual l y sul furi c (H
2
SO
4
), oxal i c
(H
2
C
2
O
4
), or phosphori c (H
3
PO
4
) aci ds], deep pores can
form,
25
wi th di ameters varyi ng between 5 and 100 nm
and l engths up to several mi crons. The bottom of each
pore al so consi sts of a thi n barri er l ayer (10-100 nm
thi ck) over the metal l i c Al surface; the pore di ameter
depends on pH, anodi zati on vol tage, and choi ce of aci d.
Thi s porous structure has been cal l ed pore-type fi l m
(PTF) or al umi te.
2,3,11
The morphol ogy of PTF i s
shown i n Fi gure 1.
26,27
Nonporous barri er oxi des can form i n several val ve
metal s, i .e., i n metal s (Al , Bi , Sb, Ta) that act as di odes
or recti fi ers after the oxi de l ayer has grown; some other
metal s have an i ncompl ete val ve effect (Ag, Cd, Fe,
Mg, Si , Sn, W, Zn, and Zr).
8
Among the val ve metal s,
pores are known to form i n Al anodi zed i n strong aci ds
and i n Si anodi zed i n hydrofl uori c aci d,
28-31
but the
* To whom i nqui ri es shoul d be addressed.

Present address: Headway Technol ogi es, 497 South Hi l l vi ew

Dri ve, Mi l pi tas, CA 95035.

Present address: HMTTechnol ogy, 1055 Page Ave., Fremont, CA

94538.
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2470 Chem. Mater. 1998, 10, 2470-2480
S0897-4756(98)00163-X CCC: $15.00 1998 Ameri can Chemi cal Soci ety
Publ i shed on Web 08/13/1998
mechani sm for pore formati on i n Si , where the pores
are wi ne-bottl e shaped, i s not understood.
32
The PTF i n Al form channel s on the surface of the Al
substrate. I n the past 70 years, conventi onal anodi za-
ti on yi el ded onl y an approxi matel y hexagonal arrange-
ment of these pores. Several mechani sms for pore
growth i n Al PTF have been proposed.
2-4,33,37
Thomp-
son, Wood, and co-workers proposed
3
that pore nucl e-
ati on i s due to a cracki ng and sel f-heal i ng of the oxi de
l ayer atop preexi sti ng ri dges on the Al surface and that
thi s forms a barri er l ayer of nonuni form thi ckness.
2,34
Masuda and co-workers have grown an al umi te fi l m
wi th a perfect hexagonal pore arrangement over a l arge
area (mi cron scal e),
23,24
by fi rst anodi zi ng Al for more
than 10 h, di ssol vi ng al umi na fi l m, and then fi nal l y
reanodi zi ng for a few mi nutes. Thi s has been re-
peated.
21,35
Recently Masuda and co-workers also formed
a patterned Si C surface by el ectron beam l i thography
and used thi s pattern to nanoi ndent the Al surface at
the correct spaci ngs pri or to anodi zati on i n aci d,
yi el di ng a perfect hexagonal al umi te pattern 2 mm 2
mm.
36
Hexagonal orderi ng was al so obtai ned duri ng a
hi gh current densi ty el ectropol i shi ng step;
10
systemati c
vari ati on of the el ectropol i shi ng ti me and vol tage es-
tabl i shed experi mental l y the regi ons of stabi l i ty of
hexagonal patterns, random patterns, and stri ped pat-
terns.
10
A theoreti cal mechani sm for hexagonal order-
i ng was devel oped.
37
We studi ed the preparati on
18
and magneti zati on
decay of R-Fe nanowi res el ectropl ated i n al umi te
19,20
and
confi rmed the formati on of hi ghl y ordered pores.
21
I n
secti ons 2 and 3 we present new experi mental observa-
ti ons about pore nucl eati on and growth. Secti on 4
revi ews the phenomenol ogi cal theori es of pore forma-
ti on, whi l e seti on 5 presents mathemati cal theori es of
pore formati on. Secti on 6 cri ti cal l y compares growth
of BTF and PTF. I n secti on 7 we di scuss the chemi stry
and our own i deas for a mechani sm for pore growth.
2. Experimental Section
2.1. Al Surface Pretreatments. An Al sheet [99.997%
pure, Al fa, wi th (100) ori entati on] was fi rst degreased i n 5%
NaOH at 60 C for 30 s, ri nsed wi th dei oni zed water,
neutral i zed i n 1:1 water/HNO3 for several seconds, and then
ri nsed agai n wi th dei oni zed water. The sampl e was el ec-
tropol i shed i n perchl ori c aci d-ethanol sol uti on (165 mL 65%
HCl O4, 700 mL of ethanol , 100 mL of 2-butoxyethanol (butyl
cel l usol ve), and 137 mL of H2O) at a current densi ty >500
mA cm
-2
for 1 mi n at <10 C. After el ectropol i shi ng, the
sampl e was washed wi th warm dei oni zed water and then
ri nsed i n col d dei oni zed water.
2.2. Anodization. Si nce the pore si ze i s l arger, but the
pore growth rate i s sl ower i n H3PO4 than i n H2C2O4,
3
we chose
H3PO4 for pore nucl eati on studi es and H2C2O4 for the pore
growth studi es.
I n the pore nucl eati on studi es, the pretreated Al sampl es
were anodi zed at a constant current densi ty of 5 mA cm
-2
(Fl uke Model 341A) i n 4% H3PO4 at room temperature for a
short ti me, usi ng an Al counter el ectrode. The anodi c al umi na
fi l ms were di ssol ved i n a mi xed sol uti on of 0.2 M H2CrO4 and
0.4 M H3PO4 for 15 mi n at 60 C.
For the studi es of pore orderi ng, anodi zati on was performed
at 40 V dc i n 3% H2C2O4 (Al dri ch) at ei ther 0 or 15 C, i n a
constant-temperature bath (Fi sher I sotemp 1016D). We modi -
fi ed Masuda and Fukudas process,
23,24
as fol l ows: (1) anodi zed
a pol i shed Al sheet for 5-10 mi n to el i mi nate l arge ri dges and
to texture the Al surface; (2) di ssol ved away the oxi de fi l m
i n a mi xed sol uti on of 0.2 M H2CrO4 and 0.4 M H3PO4 at 60
C for, typi cal l y, 5 mi n; (3) anodi zed for 0.5-12 h, to create
l ong-range orderi ng; (4) removed oxi de fi l m (opti onal l y, re-
peated steps 3 and 4); and (5) anodi zed Al agai n under the
same condi ti ons, but onl y for 3 mi n. I n step 5 the Al sheet
becomes a templ ate for growi ng hi ghl y ordered pores.
23,24
(31) Parkhuti k, V. P.; Al bel l a, J. M.; Mart nez-Duart, J. M.; Gomez-
Rodr guez, J. M.; Baro, A. M.; Shershul sky, V. I . Appl. Phys. Lett. 1993,
62, 366.
(32) Mart nez-Duart, J. M.; Parkhuti k, V. P.; Guerrero-Lemus, R.;
Moreno, J. D. Adv. Mater. 1995, 7, 226.
(33) Parkhui ti k, V. P.; Shershul sky, V. I . J . Phys. 1992, D25, 1258.
(34) Shi mi zu, K.; Kobayashi , K.; Thompson, G. E.; Wood, G. C.
Philos. Mag. 1992, A66, 643.
(35) Jessensky, O.; Mul l er, F.; Gosel e, U. Appl. Phys. Lett. 1998,
72, 1173.
(36) Masuda, H.; Yamada, H.; Satoh, M.; Asoh, H.; Nako, M.;
Tamura, T. Appl. Phys. Lett. 1997, 71, 2770.
(37) Yuzhakov, V. V.; Chang, H.-C.; Mi l l er, A. E. Phys. Rev. 1997,
B56, 12608.
Figure1. I deal hexagonal al umi te, or PTF. Metal l i c Al , on
the bottom, i s covered by an i mpervi ous barri er oxi de, of
thi ckness db, and then by a hexagonal array of pores of
di ameter Dp, wi th a cel l (repeat) di stance Dc.
26,27
Figure 2. Vol tage-ti me (V-t) anodi zati on curve for anod-
i zati on of an Al sheet i n 4% H3PO4 at a current densi ty of 5
mA cm
-2
at room temperature. Round ci rcl es wi th l abel s (A, t
) 0 s; B, t ) 10 s; C, t ) 50 s; D, t ) 100 s; E, t ) 150 s; and
F, t ) 420 s) correl ate wi th the AFM i mages shown i n Fi gure
3.
Ordered Pores in Anodized Al
2
O
3
Chem. Mater., Vol. 10, No. 9, 1998 2471
2.3. Characterization of the Alumite Film Surface.
The surfaces of both the top of the anodi c al umi na fi l ms and
of the precurved Al surface, after removal of the anodi c
al umi na fi l ms, were studi ed by scanni ng el ectron mi croscopy
(SEM, Phi l i ps XL30), by transmi ssi on el ectron mi croscopy
(TEM, Hi tachi H-8000), and by atomi c force mi croscopy (AFM,
Di gi tal I nstruments Nanoscope I I I and Di mensi on 3000).
2.4. Stoichiometryof FilmGrowth. An experi ment was
conducted to determi ne what percentage of the current i s used
to form oxi de and what percentage of the current pl aces Al
i ons i nto sol uti on.
An Al sheet was anodi zed at 40 V and 15 C for 20 mi n i n
3% H
2C2O4. The vol ume of the el ectrol yte was 150 mL. The
Al sampl e was wei ghed on a Mettl er mi crobal ance before
anodi zati on, after anodi zati on, and after stri ppi ng the al umi te
fi l m. The el ectri cal charge used i n anodi zati on was measured
by i ntegrati ng the current versus ti me chart (wei ghi ng the
paper for the cut-out area under the curve). The porosi ty of
the al umi te fi l m was esti mated from the pore structures
measured by AFM, SEM, and TEM.
3. Results and Discussion
3.1. Pore Nucleation. An anodi zi ng curve i n 4%
H
3
PO
4
at a constant current densi ty of 5 mA cm
-2
i s
shown i n Fi gure 2. I ni ti al l y (t ) 0-2.5 mi n), the
anodi zi ng vol tage i ncreases l i nearl y wi th ti me, i mpl yi ng
a l i near i ncrease i n resi stance or a l i near growth of hi gh-
resi stance oxi de, then the rate sl ows, and a l ocal
maxi mum appears (t ) 3.2 mi n i n Fi gure 2). Thi s
behavi or has been noted before.
34
I n the i ni ti al peri od
(t ) 0-2.5 mi n) the resi stance (R) changes l i nearl y wi th
ti me; thi s i mpl i es an overal l uni form growth of a fi l m
wi th constant resi sti vi ty.
a
b
c d e
f g
Figure3. AFM tappi ng mode i mages of the Al surface i n ai r after constant-current anodi zati on (5 mA cm
-2
) for ti me t and then
stri ppi ng away of the PTF wi th phosphori c-chromi c aci ds, corrsspondi ng to l abel el ed poi nts i n Fi gure 2: (a) as-el ectropol i shed,
t ) 0, poi nt A, textured surface of area 2 m 2 m, verti cal range 10 nm; (b) zoomed-i n hi gher magni fi cati on i mage (0.2 m
0.2 m, verti cal range 3 nm) of Fi gure 3a; (c) anodi zed for t ) 10 s, poi nt B, area 2 m 2 m, verti cal range 10 nm; (d) t )
50 s, poi nt C, area 2 m 2 m, verti cal range 10 nm; (e) t ) 100 s, poi nt D, area 2 m 2 m, verti cal range 100 nm; (f) t )
150 s, poi nt E, area 2 m 2 m, verti cal range 100 nm (g) t ) 420 s, poi nt E, area 2 m 2 m, verti cal range 400 nm.
2472 Chem. Mater., Vol. 10, No. 9, 1998 Li et al.
Fi gure 3a i s an i mage of the el ectropol i shed Al surface
before anodi zati on. After el ectropol i shi ng i n perchl ori c
aci d-ethanol sol uti on, Al has an al most fl at surface,
exhi bi ti ng smal l etch pi ts and bumps, whi ch coul d be
seeds for pore nucl eati on.
Fi gure 3c-g demonstrates pore nucl eati on and de-
vel opment on the anodi c al umi num surface. Fi gure 3c
shows that the pore nucl eati on occurs at the very
begi nni ng (t ) 10 s). I t suggests that the ei ther
nucl eati on has al ready occurred duri ng el ectropol i shi ng
or that nucl eati on takes pl ace al most at the same ti me
as the barri er l ayer growth. At thi s poi nt, the surface
shows many smal l paral l el grooves at l ow magni fi cati on,
as shown i n Fi gure 3c.
The i ni ti al pore densi ty i s very hi gh, on the order of
10
10
-10
12
cm
-2
(Fi gure 3b). Fi gure 3c-g shows that
wi th i ncreasi ng ti me, the pore si ze i ncreases, but the
pore densi ty decreases: the pore i ncreases i n si ze by
mergi ng wi th adjacent pores.
Pore growth may be due to a fi el d-assi sted hydrogen
i on attack on the oxi de l ayer. I f the hydrogen i on
concentrati on i s decreased, then thi s attack wi l l be sl ow
or stop and a BTF l ayer wi l l form i nstead.
34
I ndeed,
Fi gure 4 shows an AFM i mage of an Al surface after
anodi zati on up to 60 V, under the same condi ti ons as
shown i n Fi gure 3, but the H
3
PO
4
aci d el ectrol yte was
di l uted 10 ti mes, to 0.4%H
3
PO
4
. As compared to Fi gure
3d (up to 40 V), the Al surface i s very fl at and al most
pore-free. So the hydrogen i on attack must be funda-
mental to pore nucl eati on and devel opment.
The pore-type anodi c al umi num oxi de fi l m grows i n
aci di c sol uti on, due to an el ectri c-fi el d-assi sted l ocal
chemi cal di ssol uti on at the oxi de/el ectrol yte i nterface.
Obvi ousl y, thi s l ocal di ssol uti on affects the surface
features. Si nce the chemi cal di ssol uti on i s exothermi c,
the heat produced may cause a l ocal i zed temperature
i ncrease.
3.2. Highly OrderedPoreGrowth. The pore-type
al umi na fi l ms can be grown by anodi zi ng Al at constant
current or constant vol tage. For growi ng the fi l ms wi th
a desi red pore di ameter, the constant vol tage mode i s
usual l y empl oyed. Fi gures 5 and 6 show the anodi za-
ti on curves (j-t and V-t) of a textured Al sheet at
constant vol tage of 40 V i n 3% H
2
C
2
O
4
at 15 C. The
sol i d l i ne shows the fi rst-ti me anodi zati on curve; the
dotted l i ne shows the second-ti me anodi zati on (after
stri ppi ng of the oxi de and formati on of a textured
surface
23,24
).
The al umi na fi l m grows di fferentl y on the fl at Al sheet
(fi rst anodi zati on) than on the textured surface (second
anodi zati on). Fi rst, the mi ni mum j i s l arger for the
textured Al sheet than for the fl at Al sheet. Next,
there i s no current overshoot for the textured Al sheet.
Last, i n Fi gure 6 the vol tage i ncreases more sl owl y wi th
ti me (t ) 0-12 s) for the second anodi zati on than for
the fi rst anodi zati on (the di fference i s reproduci bl e, but
barel y above the error of measurement).
Si nce the textured surface shows a sl i ghtl y sl ower
i ncrease of the vol tage than the fl at Al sheet, the
al umi na l ayer formed i n ai r may be nonuni form. The
thi nnest oxi de l ayer i s probabl y at the bottom of each
curvature, where the resi stance i s l owest and el ectri c
fi el d i s the hi ghest. So the pore nucl eati on i s easi er on
a textured surface, whi ch resul ts i n a l ower barri er
l ayer growth rate. For the same reason, the pore growth
current i ncreases earl i er for the textured surface sampl e.
Therefore, for the textured surface sampl e the mi ni mum
current densi ty i s hi gher and there i s no overshoot i n
Fi gure 5.
3.3. SEM Images of Ordered Pores. A perfect
hexagonal arrangement of the pores was obtai ned when
Figure 4. AFM tappi ng mode i mage (2 m 2 m) of Al
surface after anodi zati on up to 60 V i n 0.4% H3PO4 at a
constant current densi ty of 5 mA cm
-2
at room temperature
Figure5. Current-ti me anodi zati on curve (j-t) for anodi za-
ti on i n 3% H2C2O4 at 40 V and 15 C (constant-vol tage mode).
Figure 6. Vol tage-ti me anodi zati on curve (V-t) i n 3%
H2C2O4 at 15 C. The constant-vol tage mode i s reached after
12-13 s.
Ordered Pores in Anodized Al
2
O
3
Chem. Mater., Vol. 10, No. 9, 1998 2473
anodi zati on was conducted for a l ong ti me. Fi gure 7
shows the SEM i mages obtai ned after a fi rst anodi zati on
of 10 mi n, a second anodi zati on of 11.5 h, and a thi rd
anodi zati on of 3 mi n (the oxi de was stri pped away after
the fi rst and second anodi zati ons). At l ow magni fi cati on
(Fi gure 7b), thi s ordered structure shows domai n struc-
tures wi th an average si ze of about 4 m
2
.
The domai n structures shoul d be a functi on of ti me.
That means the domai n can grow duri ng anodi zati on
(Fi gures 9 and 10). At l east two ki nds of defects were
found i n the domai ns, such as poi nt defects and mi sfi t
di sl ocati ons (Fi gure 9). There were some l arge i sl ands
(poi nt defects), i n the domai n; each i sl and was sur-
rounded by more than three pores. On the other hand,
the mi sfi t di sl ocati on of the pores l i ne al so i nterrupted
the peri odi c arrangement of the pores (Fi gure 9).
The domai n boundari es are al so shown i n Fi gure 10:
the pores gradual l y merged al ong the boundari es.
Maybe the bottoms of the pores coul d move around, and
the domai ns grew by al i gnments and mergers of pores
at domai n boundari es, i .e., the domai n si ze was a
functi on of ti me. The domai n areas were determi ned
by fi rst outl i ni ng the boundari es of several domai ns on
SEM mi crographs, counti ng the number of pores for
several domai ns, converti ng these numbers to areas,
and averagi ng. The average domai n area was a l i near
functi on of the ti me (Fi gure 11): thi s i s very si mi l ar to
grai n growth i n metal s and al l oys. For metal s and
al l oys, the dri vi ng force of grai n growth i s the grai n
boundary energy per uni t area. For grai n growth at a
fi xed temperature, the average radi us R of the grai n i s
a functi on of the ti me t:
where B i s a temperature-dependent parameter and n
i s about 0.5-0.4.
38
Thi s empi ri cal equati on i s al so sui tabl e for domai n
growth i n anodi c al umi na fi l ms (Fi gure 11). As the
pores moved and merged, the ori entati on of adjacent
(38) Tu, K.; Mayer, J. W.; Fel dman, L. C. Electronic Thin Film
Sciencefor Electrical Engineers and Materials Scientists; Macmi l l an
Publ i shi ng Comp.: New York, 1992; p 370.
Figure 7. SEM i mages of anodi c al umi na fi l ms anodi zed at
40 V i n 3% H2C2O4 at 15 C three ti mes: for 10 mi n, then
11.5 h, and then 3 mi n (the oxi de i s stri pped away after the
fi rst and second anodi zati on): (a) hi gh magni fi cati on, (b) l ow
magni fi cati on.
Figure 8. Cross-secti onal TEM mi crograph of al umi te and
Al metal bottom.
Figure 9. SEM i mage showi ng defects i n the domai n struc-
tures; the smal l arrows i ndi cate poi nt defects. Latti ce mi s-
matches can al so be seen.
R ) Bt
n
(1)
2474 Chem. Mater., Vol. 10, No. 9, 1998 Li et al.
domai ns coul d change gradual l y, so domai ns smoothl y
matched each other.
3.4. AFMImagesof OrderedPores. The best way
to understand pore growth woul d be to l ook at the oxi de/
el ectrol yte i nterface, but no nondestructi ve method can
do thi s i n ai r at the present ti me. The metal /oxi de
i nterface i s cl ose to the oxi de/el ectrol yte i nterface and
may be sensi ti ve to changes at the oxi de/el ectrol yte
i nterface, i .e., at the other si de of the barri er oxi de l ayer.
SEM i mages of the top of the surface cannot probe
di rectl y the bottom of the pores. One can remove the
amorphous oxi de growth and peer bel ow i t by AFM.
Fi gure 12a shows the top of anodi c oxi de fi l m after
reanodi zi ng, for the same sampl e as shown i n Fi gure 7:
the AFM pattern was the same as seen by SEM. Fi gure
12b shows the AFM i mage after removi ng the anodi c
oxi de fi l m: now we see the bottom of the pores (pl us
any oxi de grown from exposure to ai r). Agai n we see
the fami l i ar, hi ghl y ordered, hexagonal pattern.
The cross-secti onal anal ysi s of the AFM i mage (Fi gure
13) shows that the Al surface i s curved, wi th a radi us
of curvature of about 60-65 nm. The i nteresti ng
feature i n Fi gures 12b and 13 i s that each pore (or
scal l op) of about 100 nm di ameter and 28 nm depth
i s surrounded by si x bumps of about 20 nm di ameter
and about 10-13 nm hei ght. The l ack of ci rcul ar
symmetry of the al umi num oxi de around each scal l op
and the presence of si x bumps has not been reported
before. Each scal l op i s surrounded by si x bumps, and
each bump i s surrounded by three scal l ops. Al so, there
i s a groove or pass between nearest nei ghbor bumps.
3.5. Stoichiometry of Film Growth. We found
that duri ng anodi zati on i n 3% H
2
C
2
O
4
aci d at 40 V,
about 30% of the al umi num i s di ssol ved i nto the
el ectrol yte.
An Al sample was weighed before anodization (317 769
( 2 g), after anodi zati on (318 191 ( 2 g), and after
stri ppi ng the al umi te fi l m (316 440 ( 2 g). The
el ectri cal charge transferred duri ng anodi zati on, 14.4
C, was obtai ned by i ntegrati ng the area under the
current versus ti me curve. Thi s charge converted 1329
mg of Al i nto 1751 mg of Al
2
O
3
wi th a current effi ci ency
of 100 [14.4 C 26.98 g mol
-1
/(3 el ectrons (Al atom)
-1
96 485 C mol
-1
)/0.001 329 g] ) 99.3%. The percent
yi el d of anhydrous Al
2
O
3
was (100 0.001751 26.98)/
[0.001329 (0.5 26.98 + 1.5 15.9994)] ) 69.73%.
Thi s yi el d was al so esti mated by cal cul ati ng the fi l m
porosi ty. From the measured pore di ameter D
p
) 60
nm, cel l si ze D
c
) 104 nm (mi ni mum pore-to-pore
di stance), and pore densi ty d ) 1.118 10
10
pores cm
-2
,
the porosi ty r ) (area of pores)/(fi l m area) ) (D
p
/2)
2

1.118 10
10
)0.316, i mpl yi ng that 68.4%of the surface
was covered by al umi na. I f the pore arrangement was
exactl y hexagonal i n the whol e fi l m, the porosi ty woul d
Figure 10. Domai n boundari es and pore mergi ng al ong the
domai n boundari es. The arrows show the mergi ng of pores.
Figure 11. Domai n growth as a functi on of anodi zi ng ti me
at 40 V i n 3% H2C2O4.
a
b
Figure12. AFM i mages of (a) surface of anodi c al umi na fi l m
grown at 40 V i n 3% H2C2O4 at 15 C (oxi de thi ckness about
300 nm) (1 m 1 m, verti cal scal e 80 nm) and (b) surface
of Al substrate after the 300 nm thi ck anodi c al umi na fi l m
was stri pped away wi th H3PO4 and H2CrO4 (1.5 m 1.5 m,
verti cal scal e 80 nm).
Ordered Pores in Anodized Al
2
O
3
Chem. Mater., Vol. 10, No. 9, 1998 2475
be r ) /3.464 (D
p
/D
c
)
2
) 0.302, and the el ectrochemi -
cal yi el d was 100 (1-0.302) ) 69.8%. Both resul ts
were very cl ose to the el ectrogravi metri c esti mate of
69.73% for anhydrous Al
2
O
3
.
The 30-31% l oss of Al to the aci di c sol uti on i s
i mportant, because i f al l Al atoms were converted to
Al
2
O
3
, there woul d be a 70% i ncrease of vol ume. The
theoreti cal Pi l l i ng-Bedworth rati o (PBR)
39
i s [(26.98 +
3.0 15.994) g/2 3.0 g cm
-3
]/[ 26.98 g/2.7 g cm
-3
] )
1.70 for Al f Al
2
O
3
; such a l arge rati o i mpl i es l arge
stresses and buckl i ng of the i nterfaci al regi on. I f 31%
of the Al i s l ost to sol uti on, however, the effecti ve PBR
becomes 1.70 0.69 ) 1.18. Lower val ues, cl oser to
1.0, have been measured el sewhere.
28
3.6. Local Temperature Increase. That temper-
ature i ncreases duri ng anodi zati on can be proved by
measuri ng a j-t anodi zi ng curve whi l e the sti rri ng of
the el ectrol yte i s stopped and then restarted (Fi gure 14).
I f the reacti on heat cannot be di spersed, then the
temperature must i ncrease and accel erate ei ther chemi -
cal di ssol uti on or oxi de formati on. I ndeed, when sti r-
ri ng was stopped, the current densi ty i ncreased (Fi gure
14) and then resumed i ts previ ous val ue when sti rri ng
was restarted. I ncreasi ng the bath temperature i n-
creases the current densi ty, as seen i n Fi gure 15.
3.7. Anodization at High Voltages. The reacti on
rate was strongl y affected by the vol tage (Fi gure 16).
The current densi ty i ncreased exponenti al l y wi th the
vol tage; at 60 V the current densi ty showed l arge
fl uctuati ons. After anodi zi ng at 60 V and stri ppi ng the
oxi de, the Al surface was found to be very rough.
At hi gh vol tages, the chemi cal di ssol uti on rate at the
oxi de/sol uti on i nterface i ncreases, as does Joul e heati ng.
Local temperatures may ri se at the pore bottoms and
stresses and rates of heat di ssi pati on may become
nonuni form, thus causi ng fl uctuati ons i n the anodi zi ng
current.
3.8. Stresses in PoreGrowth. Stresses (compres-
si ve and tensi l e) i n oxi de fi l ms have been wi del y
di scussed, parti cul arl y for BTF.
2,40,41
From strai n mea-
surements, for an Al sampl e wi th an oxi de grown i n 0.1
M H
2
SO
4
at <0.5 mA cm
-2
, the oxi de i s under compres-
si ve stress, whi l e at hi gher current densi ti es (3.5-5.3
mA cm
-2
) there i s a l arge tensi l e stress.
40
3.9. Temperature Rise in Pore Growth. A l ocal
heati ng effect for pore growth, fi rst proposed by Kel l er
et al .,
26
has been i gnored for a l ong ti me, because the
temperature ri se at the anode i s not very hi gh (5-25
C). But thi s measured temperature ri se may not
represent the real l ocal temperature at the bottoms of
the pores; a l arge l ocal heati ng, due to Joul e heati ng
and l ocal oxi de di ssol uti on, coul d rai se the temperature
and i ntroduce a l arge thermal stress i n the barri er l ayer
and at the metal /oxi de i nterface.
(39) Pi l l i ng, N. B.; Bedworth, R. E. J . I nst. Metals 1923, 29, 529.
(40) Nel son, J. C.; Ori ani , R. A. Corrosion Sci. 1993, 34, 307.
(41) Young, L. J . Electrochem. Soc. 1963, 110, 589.
Figure13. Cross-secti on AFM anal ysi s of scal l ops wi thi n a domai n: (l eft) enl arged detai l of the AFM of Fi gure 12b; (top ri ght)
hei ght profi l e through the tops of the barri er oxi de bumps and the bottoms of the pores, corrspondi ng to the di agonal l i ne on
l eft; (bottom ri ght) hei ght profi l e through the passes between the bumps of oxi de and the bottom of the pores, correspondi ng
to the al most hori zontal l i ne on l eft.
Figure14. The effect of sti rri ng on the current densi ty at 40
V i n 3% H2C2O4 at 15 C.
2476 Chem. Mater., Vol. 10, No. 9, 1998 Li et al.
An el ementary one-di mensi onal cal cul ati on
22
of the
possi bl e heat ri se at the bottom of the pores of PTF
assumes that the el ectri cal current concentrates at the
pore bottom. Joul e heati ng, due to el ectri cal power
di ssi pati on wi thi n the hi gh-resi stance barri er oxi de
l ayer, i s much l arger than the exothermi ci ty of the
chemi cal reacti ons.
42
Usi ng a Lapl ace transform and a
numeri cal method, to i ntegrate the equati on for thermal
conducti vi ty i n a semi -i nfi ni te regi on of the el ectrol yte,
the cal cul ated temperature change i s ) 1.823/
p[0.2629 + 3.07(C
p
)
1/2
],
22,43
where p i s the porosi ty,
i s the thermal conducti vi ty of the oxi de, and C
p
i s i ts
heat capaci ty. The esti mated temperature ri se wi thi n
the el ectrol yte for the fi rst 12 s, at bottom of the pore,
i s (cal c) ) 21 C.
22
Thi s resul t di sagrees wi th a
previ ous steady-state cal cul ati on of (cal c) )0.06 C,
42
but agrees wi th an experi mental temperature ri se of the
anode temperature of (exp) ) 25 C.
44
4. Phenomenological Theories of Pore
Formation
Before presenti ng our own suggesti ons for a possi bl e
mechani sm of pore formati on i n secti on 7, we revi ew i n
secti ons 4 and 5 what has been proposed i n the
l i terature; i n secti on 6 we compare and contrast barri er
type fi l ms and pore-type fi l ms, because some i nsi ght i nto
a mechani sm for PTF may be found here. I n secti on 7
we gather tentati ve concl usi ons, some buttressed by our
own observati ons, about pore-type fi l ms.
Earl y theori es of porous oxi de formati on were re-
vi ewed,
4
wi th a thought that theori sts have been sl ow
i n expl ai ni ng how or why the qui te remarkabl e uni form
spati al di stri buti on of pores came about i n the fi rst
pl ace, nor why i t i s so speci fi cal l y rel ated to the
formati on vol tage.
4
The ranges of pore di ameters and cel l di ameters i n
PTF are much l arger than any crystal l ographi c peri od-
i ci ty or any reasonabl e supercel l si ze for ei ther Al or
any of i ts oxi des; therefore, i t i s cl ear that the formati on
of al umi te i s not a crystal growth phenomenon. Regul ar
arrays of cel l s (l amel l ar and rod eutecti cs, e.g. pearl i te)
can al so form duri ng the sol i di fi cati on of l i qui ds,
45-47
but these structures have 10 mm scal es; therefore i t i s
al so cl ear that l i qui d-sol i d i nstabi l i ti es wi l l not expl ai n
PTF ei ther.
Marangoni orderi ng may occur i n the sol uti on above
the pores.
48,49
[The Marangoni effect i s an i nterfaci al
surface tensi on effect between two l i qui ds (whi ch ex-
pl ai ns
48
the ol d Benard probl em
50-52
)]. I t i s not known
whether a Marangoni mechani sm i s operati ve i n PFT
formati on. Once the pores form, thei r evol uti on can be
model ed by Monte Carl o techni ques (Voronoi di a-
grams),
53,54
but thi s sheds no l i ght on why or how the
pores form.
I t has been suggested that, at the bottom of the pores,
the pH drops preci pi tousl y, i ncreasi ng the sol ubi l i ty of
the oxi de; thi s i s an autocatal yti c mechani sm of pi t
propagati on.
6,55,56
There may be a pronounced tem-
perature and concentrati on di fferenti al between the
pore base and the bul k el ectrol yte.
4,44
The cracks on
the surface of the ai r-formed oxi de l ayer can al so be
centers for pore nucl eati on,
34
but they are unl i kel y to
be a major factor, because of thei r l ow densi ty.
Thompson and Wood
3
assumed the fol l owi ng mecha-
ni sti c sequence: (1) el ectropol i shi ng or other pretreat-
ment l eft a sl i ghtl y scal l oped surface of al umi num
covered by oxi de; (2) a scal l oped nati ve barri er oxi de
fi l m grew over thi s scal l oped surface; (3) as anodi zati on
started, pores woul d start at cracks and i mperfecti ons
i n the surface, l eavi ng an el ectri c fi el d concentrated
bel ow the regi ons where the oxi de fi l m was thi nner, thus
(4) ai di ng the l ocal di ssol uti on of oxi de; (5) thi s new pore
(42) Nagayama, M.; Tamura, K. Electrochim. Acta 1968, 13, 1773.
(43) Carl saw, H. S.; Jaeger, J. C. Conduction of Heat in Solids;
Cl arendon Press: Oxford, 1959; p 76, eq 9.
(44) Mason, R. B. J . Electrochem. Soc. 1955, 102, 671.
(45) Pel ce, P., Ed. Dynamics of Curved Fronts; Academi c: New
York, 1988.
(46) Zener, C. AI ME Trans. 1946, 167, 550.
(47) R. H. Brandt, J. Appl . Phys. 1945, 16, 139.
(48) Pearson, J. R. A. J . Fluid Mech. 1958, 4, 489.
(49) Ni el d, D. A. J . Fluid Mech. 1964, 19, 341.
(50) Benard, H. J . Phys. 1900, 9, 513.
(51) Lord Rayl ei gh Philos. Mag. 1916, 32, 529.
(52) Chandrasekhar, S. Hydrodynamic and Hydromagnetic Stabil-
ity; Cl arendon Press: Oxford, 1961.
(53) Randon, J.; Mardi l ovi ch, P. P.; Govyadi nov, A. N.; Paterson,
R. J . Colloid I nterfaceSci. 1995, 169, 335.
(54) Ani s, D.; Bhattacharya, B. K. Adv. Computing Res. 1983, 1,
159.
(55) Hoar, T. P. ElectrodeProcesses; Butterworths: London, 1961;
p 299.
(56) Vetter, K. J.; Strehbl ow, H. H. I n Localized Corrosion; Staehl e,
R. W., Brown, B. F., Kruger, J., Agrawal , A., Eds.; Nati onal Assoc.
Cor. Engrg: Houston, 1974; p 240.
Figure15. The effect of the bath temperature on the current
densi ty at 40 V i n 3% H2C2O4.
Figure16. The effect of vol tage on the current densi ty i n 3%
H2C2O4 at 15 C.
Ordered Pores in Anodized Al
2
O
3
Chem. Mater., Vol. 10, No. 9, 1998 2477
bottom deepened, and a major pore formed, at the
expense of the former shal l ow pores.
3
At the metal /
oxi de i nterface the average fi el d across the barri er l ayer
determi ned the barri er fi l m growth rate, whi l e at the
oxi de/el ectrol yte i nterface the l ocal fi el d at the pore
bottom, assi sted by l ocal heati ng, determi ned the oxi de
di ssol uti on rate.
3
The fi l m growth rate was approxi -
matel y constant and i ndependent of pore bottom cur-
vature, whi l e the di ssol uti on rate i ncreased as the pore
base radi us of curvature decreased. As the pore radi us
of curvature decreased, the fi l m di ssol uti on rate i n-
creased, to enl arge the pores; i f the pore radi us became
too bi g, the di ssol uti on sl owed and the pores tended to
fi l l ; these two competi ng processes kept the pore radi us
constant.
3
5. Mathematical Theories of Pore Formation
Parkhuti k and Shershul sky presented a ki neti c theory
for si ngl e-pore growth.
33
They assumed that the el ectri c
fi el d i n the scal l opped barri er oxi de at the bases of each
pore was i nhomogeneous both l ateral l y (i .e. al ong the
oxi de surface) and al so i nwardl y (i .e. wi thi n the oxi de
l ayer) and that the depth dependence of E was due
mostl y to the nonpl anari ty of the i nterfaces.
33
By
assumi ng a hemi spheri cal pore bottom, they found that
the pore radi us, R
m
, i s a functi on of the appl i ed
potenti al , U
o
,
33
where k i s a functi on of oxi de formati on and oxi de
di ssol uti on rate constants k
ox
and k
di ss
and of three
parameters, R, , and ,
and that R
m
i s al so a functi on of pH
where R
mo
i s the pore radi us extrapol ated to pH 0.
33
These equati ons
33
for R
m
reproduced the experi mental
57
l i near dependence of the pore radi us R
m
on vol tage U
o
and al so the experi mental
57
quasi l i near dependence of
pore radi us R
m
on pH. Thi s theory mai ntai ned the
assumed i ni ti al hemi spheri cal shape for a pore bottom
33
but di d not expl ai n how thi s shape started, nor di d i t
expl ai n the hexagonal orderi ng of the pores.
A theoreti cal effort attempted to prove the curved
growth front i n porous Si .
58
A recent theory of pattern formati on duri ng el ectro-
pol i shi ng of al umi num
10,37,59
proposed that the curved
barri er oxi de forms because mol ecul es of ethanol (the
majori ty consti tuent of a commerci al el ectropol i shi ng
sol uti on) adhere preferenti al l y al ong the ri dges of the
oxi de, rather than on the pore bottoms; thi s adhesi on
woul d faci l i tate i ncreased corrosi on at the rel ati vel y
more exposed pore bottoms.
10,37
Pore growth i nvol ves heati ng.
44,60
Temperature i n-
creases between 1 and 25 K have been measured;
3
a
cal cul ati on esti mated that 84% of the heat i s produced
by l ocal Joul e heati ng but predi cted onl y a smal l
temperature ri se (<1 K) i n the el ectrol yte at steady
state.
42
A l arge temperature ri se (25 K) was cal cul ated
at the pore bottom i n the absence of convecti on.
22
6. Comparison of Growth of PTF and BTF
A successful theory for organi zed pore growth of
al umi te shoul d start from the sal i ent di fferences be-
tween Al anodi zati on i n basi c or at neutral pH (BTF,
where no pores grow, al though they may form), and
anodi zati on at aci di c pH (PTF, where pores form and
grow effi ci entl y).
(1) For BTF, the Faradai c current effi ci ency i n bui l d-
i ng oxi de i s hi gh (cl ose to 100%); the metal /oxi de and
oxi de/sol uti on i nterfaces remai n pl anar; the current
decays exponenti al l y wi th ti me; some pores may form
at the oxi de/el ectrol yte i nterface, but do not grow. For
PTF, the Faradai c effi ci ency i n maki ng oxi de i s l ower
(70%or bel ow); both the metal /oxi de and oxi de/sol uti on
i nterfaces become curved (spheri cal segments); the
current ri ses dramati cal l y, unti l a steady-state current
i s reached. The barri er oxi de l ayer conti nuousl y regen-
erates at the pore bottoms but retai ns a smal l but
constant thi ckness. The pore wal l s consi st of amor-
phous Al
2
O
3
, some conjugate ani ons of the formi ng aci ds
(up to 20%), smal l amounts of water, and some nano-
crystal l i tes. The pore di ameter i s uni form; the pore
hei ght i ncreases l i nearl y wi th ti me.
(2) The l arge overpotenti al i n the formati on of PTF
(about 10-150 V) may generate hi ghl y l ocal i zed Joul e
heati ng at the oxi de/el ectrol yte i nterface. The barri er
l ayer at the bottom of the pores i n PTF i s a di el ectri c,
wi th a l arge potenti al drop across i t. The l ocal el ectri c
fi el d i s on the order of MV cm
-1
. I n BTF about 10% of
the i ons may be mobi l e.
8
(3) I n PTF Joul e heati ng, the overvol tage and the hi gh
current densi ty at the oxi de/el ectrol yte i nterface, to-
gether wi th the exothermi c aci d-catal yzed al umi na
di ssol uti on, may rai se the l ocal temperature. The
i ncrease i n anode temperature was measured by several
authors
44,60
and esti mated to be smal l by a cal cul ati on
of the steady-state temperature i n the el ectrol yte;
42
a
l arger temperature ri se i s esti mated i n the absence of
convecti on.
22
(4) For PTF growth at the bottom of the pores, Al
3+
i ons mi grate from the metal across the metal /oxi de
boundary i nto the barri er oxi de; O
2-
i ons are formed as
O
2-
(oxi de) from water at the oxi de/el ectrol yte boundary
and mi grate i nto the barri er l ayer. Roughl y 30%of the
Al
3+
i ons i n the oxi de di ssol ve i nto the el ectrol yte, wi th
an addi ti onal rel ease of l ocal heat: thi s di ssol uti on i s
aci d-catal yzed. The two sources of the protons requi red
for thi s di ssol uti on are the bul k el ectrol yte (but these
protons must move agai nst the appl i ed potenti al ) and
the protons l i berated when water spl i ts at the oxi de/
el ectrol yte surface to produce O
2-
(oxi de).
(5) I n PTF, the vol ume change, due to oxi de formati on
and to thermal expansi on, may i ntroduce stresses
wi thi n the barri er l ayer.
(6) I n PTF (but not i n BTF), a curved metal /oxi de
i nterface i s somehow formed; a si mi l ar curved i nterface
forms at the oxi de/el ectrol yte i nterface.
(57) Ebi hara, K.; Takahashi , H.; Nagayama, M. J . Met. Finish. Soc.
J pn. 1982, 33, 4.
(58) Zhang, X. G. J . Electrochem. Soc. 1991, 138, 3750.
(59) Yue, D.-F., Ph.D. Di ssertati on, Notre Dame Uni versi ty, 1995.
(60) Appl ewhi te, F. R.; Leach, J. S.; Neufel d, P. Corros. Sci. 1969,
9, 305.
R
m
) -U
o
/E
eo
(1 - k) l n(1 - k) (2)
k ) 1 - [(/)(k
ox
/k
di ss
- 1)/(1 + k
ox
/Rk
di ss
)]
1/2
(3)
R
m
) R
mo
/{1-2.3 pH [l n(RA
o
k
di ss
/Bk
di ss
)]
-1
} (4)
2478 Chem. Mater., Vol. 10, No. 9, 1998 Li et al.
(7) I n PTF, a hexagonal orderi ng of both the pores
and of the pi l l ars made of amorphous Al
2
O
3
sets i n
i ni ti al l y at cri ti cal ti mes and vol tages of el ectropol i sh-
i ng
10,37
or can be i nduced by l ong-term anodi zi ng,
21,24
by repeti ti ve anodi zati on/stri ppi ng cycl es, or by nanoi n-
denti ng wi th a Si C templ ate at the ri ght spaci ngs.
36
7. Proposed Mechanismof Pore Formation
We now provi de, i n 15 poi nts, a possi bl e mechani sm
for pore formati on. Poi nts 1-8 are rel ati vel y sel f-
evi dent suggesti ons based on the overal l chemi stry.
Poi nts 9-15 are i nsi ghts or concl usi ons based on our
own resul ts.
Duri ng PTF formati on, hydrogen i ons and the el ectri c
fi el d at the oxi de/el ectrol yte i nterface must pl ay i mpor-
tant rol es.
(1) El ectropol i shi ng fl attens some l arge surface i r-
regul ari ti es, but al so creates
62
a l arge number of smal l
pores (Fi gure 3a). Fi gure 3a shows pi t si zes from a few
to tens of nanometers and a pi t densi ty of about 10
10
-
10
12
pi ts cm
-2
. Some of these pi ts can devel op i nto pore
nucl ei . Thei r densi ty wi l l decrease as pores grow,
because pores merge as anodi zi ng ti me i ncreases.
The thi ckness of an ai r-formed oxi de l ayer may be
smal l but nonuni form, supporti ng a huge el ectri c fi el d
gradi ent (several MV cm
-1
) across i t. I n PTF, the
el ectri c fi el d and the i oni c current densi ty shoul d be
l arger at the pore bottoms than between the pores.
3
(2) For both PTF and BTF, Al
3+
i ons form at the
metal /oxi de i nterface
and mi grate i nto the oxi de l ayer.
(3) For both BTF and PTF, at the oxi de/el ectrol yte
i nterface the water-spl i tti ng reacti on
occurs and i s rate-determi ni ng.
6,61
The O
2-
(oxi de) i ons
mi grate, thanks to the el ectri c fi el d, wi thi n the oxi de
from the oxi de/sol uti on i nterface toward the metal /oxi de
i nterface, to form Al
2
O
3
. The oxi de formati on rate
constant k
ox
of ref 33 must be the rate for eq 5 or 6,
whi chever i s sl ower.
(4) I n BTF, and parti cul arl y i n base, the protons or
hydroni um i ons generated by the water-spl i tti ng reac-
ti on are neutral i zed l ocal l y by the reacti on
(5) I n contrast, i n PTF the protons can l ocal l y di ssol ve
more oxi de:
The oxi de di ssol uti on rate constant k
di ss
of ref 33 must
be the rate for eq 7. I n secti on 3.5 we measured that
about 30% of the current produced di ssol ved speci es,
whi l e 70% of the current produced sol i d oxi de.
(6) Hydroni um i ons can al so mi grate toward the
cathode, where they l eave the el ectrol ysi s cel l as H
2
gas,
compl eti ng the ci rcui t:
(7) By charge bal ance i n PTF and BTF, the rates of
eqs 5 and 8 must be equal .
(8) Much of the oxi de produced by eq 6 constructs the
si dewal l s of the PTF. I n a PTF eq 7 wi l l be sl ower
than eq 5. The water-spl i tti ng reacti on (eq 6) wi l l
thi cken both BTF and PTF barri er fi l ms.
The mai n di fference betwen BTF and PTF i s eq 7,
whi ch must occur preferenti al l y at the pore bottom and
keep the PTF barri er oxi de thi n. The absence of eq 7
makes the BTF uni form.
62
For PTF, eq 7 must occur
preferenti al l y where the el ectri c fi el d i s hi ghest, i .e., at
the center or cl ose to the center of the pore bottom.
We now present poi nts 9-15 that are a new contri bu-
ti on of thi s study.
(9) The growth of the porous anodi c oxi de (si dewal l s)
i n PTF must now be expl ai ned. Si nce, as seen i n Fi gure
8, the pore wal l s are uni form through thei r l ength, the
key growth step must be near the pore bottom, probabl y
very cl ose to the ci rcl e of i ntersecti on between the
cyl i nder of the pore wal l and the spheri cal segment of
the pore bottom. At thi s ci rcl e of i ntersecti on the water-
spl i tti ng reacti on (eq 6) must al so occur, but eq 7 shoul d
not occur. Thus the porous oxi de can grow, fed by Al
3+
i ons from bel ow, and from O
2-
(oxi de) i ons from the
si de. Fi gure 13 seems to show that the pore thi ckness
i s not ci rcul arl y symmetri c around the pore bottom, but
thi s i s probabl y an arti fact. The di ssol uti on of the pores
by phosphori c aci d-chromi c aci d exposes the barri er
oxi de, whi ch has l umps because i ts growth i s greatest
i n the regi on farthest from three adjacent pores. Thi s
i s qui te obvi ous from the AFM profi l es of Fi gure 13.
(10) At these si des of the bottom of the pores, there
i s probabl y some competi ti on between the water-spl i t-
ti ng reacti on (eq 6) and the di ssoci ati on of aci ds to form
conjugate base ani ons,
so that the conjugate base ani ons can repl ace O
2-
i n
the oxi de, as substi tuti on or contami nati on i mpuri ti es
wi thi n some depth, as seen by the UMI ST group.
3,34
Chromi c aci d does not have a protonated conjugate base
and thus does not i ncorporate i nto the pore wal l s.
3
The
i mportance of eqs 9-11 has not, to our knowl edge, been
emphasi zed before: we can now expl ai n for the fi rst
ti me why di chromate does not i ncorporate i nto the pore
wal l s.
(11) Both BTF and PTF usual l y start from some Al
surface that i s fai rl y smooth (hi l l s of at l east 3 nm
hei ght), but wi th pi ts formed at l atti ce i mperfecti ons or
by el ectropol i shi ng (i .e. etchi ng or preanodi zati on).
These Al pi ts wi l l be covered by an ai r-formed oxi de, so
that both the metal /oxi de and the oxi de/el ectol yte
i nterfaces are l ocal l y curved. The oxi de thi ckness may
(61) Val and, T.; Heusl er, K. E. J . Electroanal. Chem. 1983, 149,
71.
(62) Shi mi zu, K.; Kobayashi , K.; Skel don, P.; Thompson, G. E.;
Wood, G. C. Corrosion Sci. 1997, 39, 701.
Al (s) f Al
3+
(oxi de) + 3e
-
(5)
3
/
2
H
2
O(l ) f 3H
+
(aq) +
3
/
2
O
2-
(oxi de) (6)
2H
+
(aq) + OH
-
(aq) f H
2
O(l )
1
/
2
Al
2
O
3
(s) + 3H
+
(aq) f Al
3+
(aq) +
3
/
2
H
2
O(l ) (7)
3H
+
(aq) + 3e
-
f
1
/
2
H
2
(g) (8)
HSO
4
-
(aq) f SO
4
2-
(oxi de) + H
+
(aq) (9)
H
2
PO
4
-
(aq) f HPO
4
2-
(oxi de) + H
+
(aq) (10)
HC
2
O
4
-
(aq) f C
2
O
4
2-
(oxi de) + H
+
(aq) (11)
Ordered Pores in Anodized Al
2
O
3
Chem. Mater., Vol. 10, No. 9, 1998 2479
be uni form or i rregul ar; i ts coverage of the Al metal
surface i s nei ther perfect nor compl ete. Thi s i s an
obvi ous concl usi on from the observati on that al umi num
i s macroscopi cal l y conducti ve despi te the oxi de coverage.
(12) As anodi zati on starts, the el ectri c fi el d at the
oxi de/el ectrol yte i nterface shoul d be greater at si tes
where the nati ve oxi de coverage i s thi nner, or el se the
metal /oxi de i nterface fl attens out i ni ti al l y, so that the
oxi de l ayer i s thi cker i n some parts of the surface,
al l owi ng the el ectri c fi el d to concentrate where the oxi de
i s thi nner. We do not yet have experi mental data that
can di scri mi nate between these two possi bi l i ti es. I n
BTF, any l ocal el ectri c fi el d i ncrease does not encounter
aci d-catal yzed oxi de di ssol uti on, and pores do not grow.
(13) I n PTF, as pore growth conti nues, a curved metal /
oxi de i nterface i s mai ntai ned or reestabl i shed at the
pore bottom, to match the curved oxi de/el ectrol yte
i nterface. Thi s constant thi ckness of the barri er oxi de
l ayer was wel l -establ i shed i n previ ous studi es, can be
seen vaguel y i n Fi gure 8, and i s very cl ear i n more
recent cross-secti onal TEM mi crographs (to be publ i shed
l ater).
(14) Once smal l pores have formed, the aci d and
el ectri c potenti al penetrate i nto the pore, and the growth
becomes sel f-catal yzi ng.
33
(15) I f the pores are not ordered, then a hori zontal
mobi l i ty of i ons i n the barri er l ayer
8
al l ows for a
reorderi ng of the pores, unti l an equi l i bri um hexagonal
orderi ng i s reached. Thi s i s a potenti al l y si gni fi cant
new concl usi on of the present study.
8. Discussion
Nanopores i n al umi num oxi di zed i n strong aci ds can
become ordered ei ther at certi an vol tages and ti mes of
the i ni ti al el ectropol i shi ng
10
or by l ong-term anodi zati on
and reanodi zati on,
24
by nanoi ndenti ng at the ri ght
posi ti ons then anodi zi ng,
36
or by the mul ti pl e reanod-
i zati on demonstrated above. Ordered pore domai ns
grow l i nearl y wi th ti me and i ncrease wi th i ncreasi ng
temperature. Si gni fi cant heati ng occurs duri ng pore
growth.
We suggest that the pores are i ni ti ated when the
el ectri c fi el d i s i ncreased i nto a shal l ow pore bottom and
i ni ti ates l ocal aci d corrosi on. The pore wal l s are gener-
ated i n a ci rcul ar ri ng around the bottom, wi th oc-
casi onal i ncorporati on of conjugate base ani ons i nto the
pore wal l s. The hexagonal orderi ng occursei ther (i ) by
an evol uti onary sel ecti on of those pore bottoms that
have the correct spaci ng
33
for the aci d and vol tage used
or (i i ) by a di ffusi on of the pore bottoms, ai ded by l ateral
mobi l i ty of the i ons that consti tute the barri er l ayer.
9. Conclusion
The fol l owi ng are the mai n concl usi ons of thi s study.
(1) Domai n structures form i n hexagonal l y ordered
anodi c al umi na fi l ms; the average domai n si zes are a
l i near functi on of ti me. The domai ns form by pores
movi ng and/or mergi ng.
(2) Pore nucl eati on i n PTF occurs as the barri er l ayer
i s fi rst formed, concentrates where the oxi de i s thi nnest,
and i nvol ves an aci d-catal yzed parti al oxi de di ssol uti on
i n PTF at the pore bottoms, where the el ectri c fi el d i s
hi ghest. Thi s aci d-catal yzed process i s absent i n BTF.
(3) Joul e heati ng and aci d-catal yzed oxi de di ssol uti on
heat the pore bottom.
(4) The hexagonal orderi ng of the pores i s not yet
expl ai ned, but the mobi l i ty of i ons wi thi n the barri er
oxi de
8
and of Al atoms wi thi n the metal may expl ai n
why pores can rearrange dynami cal l y and why l i near
domai n growth wi th ti me i s possi bl e.
Acknowledgment. Thi s work was supported by
DOD-USARO-DAA-H04-96-1-0316. We are grateful to
Prof. Wi l l i am D. Doyl e for hi s support, constructi ve
cri ti ci sm, and encouragement.
CM980163A
2480 Chem. Mater., Vol. 10, No. 9, 1998 Li et al.