Ekrrochimm Am, Vol 39, No .9n 99. 1281-1289.

1994
Pergamon Copyn& 0 1994 Ekwer Saeme Ltd
Pnnwd 111 Oreal BnWn All ngbls nserwd
0013~4666/945700+000
00134686(94)EOO48-5

INFLUENCE OF THE ANODIZING PROCEDURE ON THE

STRUCTURE AND THE PROPERTIES OF TITANIUM
OXIDE FILMS AND ITS EFFECT ON COPPER
NUCLEATION
J-L DELPLANCKE,*A GARNIER,~Y MAssIANIt and R WINAND*
*M&allur@e-Electrochume,CP165, Umversitb Llbre de Bruxelles, 50 Avenue F D Roosevelt,
B-1050 Bruxelles,Belgmm
TLaboratoire de Phyaco-Chlmie des MatCnaux, Umversltt de Provence (Aix Marseille I),
3 Place Victor Hugo, F-13331 Marserlle Cedex 3, France

(Received 5 September 1993, In retnsedform 25 November 1993)

Abstract-Thm oxide films are grown electrochenncally on commercially pure titamum substrates Con-
stant potential (potentiostatic), constant current (galvanostahc) and mitml constant current followed by
constant potential (comhned) growth modes are stu&ed The structure, the composition, the thickness,
the electrochernuzl and the -conducting properties of the oxide films are considerably mfluenced by
the growth mode even if the final anodlzlng potential has a constant value

Key words anodization, structure, properties, titanium, oxide films, copper nucleation

1. INTRODUCTION acid bath as described prevlously[24] As mentioned

The composltlon and the structure of the oxide films
produced by anodlc oxidation of titanium m sul-
phunc acid have been mvestlgated m great detd by
many researchers[l-61
Three modes are described m the literature for the
growth of these anodlc oxide films
the potentlostatlc growth mode for which a con-
stant potential vs a reference electrode 1s applied
directly to the anode,
the galvanostatlc growth mode for which a con-
stant current IS apphed to the electrochemical cell,
the combined growth mode for which a constant
current 1s first applied to the cell until the anode
potential reached a fixed value Then, this poten-
tial 1s maintained for a gven penod of time
Accordmg to the data published m the literature,
whatever the growth mode, the composition of the
film, for final anodlzmg potentials higher than 45V
1s (mlcro)crystalhne anatase and/or rutlle[7-231
Unfortunately, the same agreement does not exist for
the optical and electronic properties of these films
The purpose of this paper 1s then to study m the
same electrolyte and at the same temperature the
influence of the growth mode on the structure and
the propewes of films produced at the same final
anodizmg potential
by the producer, the mam impurity contents of
IMIllS are listed m Table 1 All the anodes have
been cut from the same titanium sheet to hmlt the
mod&ations of composltlon The other electrode
was a platinum cathode Analytical grade sulphunc
acid (Carlo Erba) was used to prepare a 1 M sul-
phurlc acid solution The electrolyte temperature
was maintained at 25°C A Philips PE 1649 dc power
supply was used
For the potentlostatlc anodlzatlon, a constant
anode-to-cathode voltage drop of 5OV was preset
mth a maximum permlsslble current density of
~l~nAm-z This constant value was mamtamed for
For the galvanostatlc anodlzatlon, a constant
current density of 1OOAm-2 was preset Hnth a
maximum permlsslble anode-to-cathode voltage
drop of 50 V
For the combined growth mode, galvanostatlc
anodization, as described above, was first performed
until the 50V anode-to-cathode voltage drop value
was reached Then this constant 50V value was
maintained for 1 mm
Table 1 Composition of the commercndly pure IMIllS
titanium samples
Impunty Content (% w/w)

Oxygen 007
Chromium 005
2. EXPERIMENTAL Manganese 005
Nickel 005
2 1 Anodtzatlon Vanadium 005
Commercially pure titanium anodes (IMIllS) Iron 0 025
Carbon 002
were chenucally polished m a hydrofluonc-mtnc

1281
1282 J -L DELPLANCKE et al
2 2 Analysts
2 2 1 Structural analyszs Surface mlcrographs of
the oxide films were obtamed by means of an optical
microscope REICHERT-JUNG MeF3A and by
means of a Scannmg Electron Microscope (SEM)
JEOL JSM 820
The structure of the films was observed at high
magmficatlon with a Transmlsslon Electron Mlcro-
scope (TEM) JEM 200CX with an accelerating
voltage of 200 kV (The oxide films were separated
from their substrates as described by Nurse et
al WI 1 static film with a smaller density of dark blue
The crystallmlty of the films was obtained by
Transmlsslon High Energy Electron Diffraction
(THEED) m the TEM The spot diameter on the
sample for the electron dlffractlon 1s about 3 pm
The elementary composltlon of the anodized tlta-
mum samples and the composltlon profile inside the
oxide films were determined by Auger analysis (PHI
32-060 A SAM)
2 2 2 Electrochemzcal propertzes The electro-
chemical properties of the oxide films were studied
by nucleating copper electrochemlcally on the anod-
ized substrates m an additive-free copper sulphate-
sulphurlc acid electrolyte at 25°C
Short-time (15 s) potential cathodic pulses with a
magnitude of + 56mV vs the standard hydrogen
electrode (she) were applied and the current
responses were recorded (see reference [26]) The
copper nuclei were observed by optical microscopy
and their positrons were correlated with the mlcro-
structures of the oxide films
2 2 3 Semrconductzng propertzes Electrochemical
impedance spectroscopy (EIS) was carried out m a
0 5 M H,SO, solution wth a 273 PAR potentiostat/
galvanostat and a PAR 5208 lock-m analyser (by
superlmposmg a 001 V UC voltage) The exposed
surface area was 4 x 10-4m2 A 10-2m2 gold
counter electrode was used The capacitance mea-
surements vs the applied potential were performed
m the cathodic direction by step of 0 1 V, starting
from 2 656 V vs she and holding the fixed potential
for 2mm before performmg the electrochemical
impedance spectroscopy Measurements of the mter-
facial capacitance were carried out m the l-40 kHz
frequency domain Using the EQUIVCRT software,
the capacitance values were calculated by fitting the
experimental values The equivalent clrcult was a
resistor m series with a capacitor (high frequency
measurements) The relative error on the capacitance
values was always lower than 3%
3. RESULTS
3 1 Structure of the anodzc oxzdejlms
Scanning electron nucroscopy reveals, for the
anodlc films grown by the three different techniques,
only the gram structure of the titanium substrates
after chemical pohshmg The oxide films do not
show differences, as a function of the anodlc growth
mode, for the reflected electrons On the contrary,
optical microscopy reveals a lot of differences for the
same samples (see Fig 1)
l the potentlostatlc anodlc oxide film presents, on
the titanium surface, a uniform pale yellow colour
Only a few grams present a very pale blue colour
l the galvanostatic anodlc oxide film presents, on
the titanium surface, a mixture of dark yellow and
pale blue grams Very fine dark blue spots are ran-
domly dispersed m the pale blue grams Slmllarly,
dark brown spots are observed m the yellow
grams but these spots seem to form clusters
l the combined anodlc oxide films presents a struc-
ture and a colour similar to those of the galvano-
spots
These macrostructures are confirmed by the TEM
experiments (after the titanium substrate
dlssolutlon) Indeed, a common feature to all the
anodlc films IS that they reproduce the gram struc-
ture of their underlying titanium substrates, but the
TEM experiments also reveal the microstructure of
the anodlc films This microstructure 1s different
according to the growth mode
l the potentiostatlc film 1s constituted of very small
crystals with a diameter rangmg from 10 to
2OOnm, homogeneously dispersed m a matrix
There 1s no difference from one gram to the other
except that these crystals are not observed at the
gram boundaries (see Fig 2a)
l the galvanostatlc film 1s heterogeneous (see Fig
2b) Some grams present a microstructure slmllar
to that observed m the potentlostatlc film Hrlth
homogeneously dispersed small crystals For other
grams, these small crystals are grouped to form
large elongated or small spherical clusters It
seems that these clusters could be correlated
respectively to the elongated clusters observed m
the yellow grams and to the dark blue spots
observed m the pale blue grams
l the combined !ilm presents microstructures very
similar to the galvanostatlc films
3 2 Composztzonof the anodzcjlms
For all the samples, the Auger analysis reveals the
presence of tltamum and oxygen with a slight surface
contammatlon with carbon and sulphur The shape
of the titanium peaks 1s characterlstlc of titanium
dioxide with the L3M2,Mz3 peak higher than the
L,M,,V peaW71
The Auger profiles reveal thm films on the tita-
mum substrates but the oxide film thickness 1s about
twice as large for the potentlostatlc film than for the
galvanostatlc and the combined films
Whatever the growth mode, the electron dlffrac-
tlon patterns show the simultaneous presence of
rutlle and anatase For the potentlostatlc film, rings
of small diffraction spots are observed, attesting the
absence of a preferential orientation for the small dlf-
fractmg crystals (see Fig 3a) The same result 1s
obtained for the galvanostatlc and the combined
films while diffracting m the grams that contam
homogeneously dispersed small crystals On the con-
trary, when the diffraction 1s performed m the grams
that contam the clusters, very intense spots supenm-
posed on the fine dlffractlon rings are observed (see
Fig 3b) Unfortunately, these spots are so intense
 Influence of the anodlang procedure 1283

Fig 1 Optical rmcroscop~es of tttamum samples anti by the three Merent modes ((a) poten-
tlostatic, (b) galvanostatx, (c) combined growth mode)
1284 J -L DELPLANCKEet aI

Potentlostatx growth modd

ialvdnostatx growth mode

2 ‘ansm~s~on electron m~croscop~es of tltamum samples anodxed by the three duffel ‘ent growth
modes ((a) potentlostatlc, (b) galvanostatlc, (c) combmed growth mode)
 Influence of t& anodlpng procedure
Electron dIffractIon patterns
Galvanostatlc anodlc oxide film on tltamum
Rg 3 Electron d&a&on analysis of the tltamum anodlc oxide tilms ((a) potentlostatic oxide film, (b)
galvanostak oxide film-dflraction in a gram contnmng clusters)
and the anatase and rutrle drffractron patterns are so
close that, with the used apparatus, rt IS rmpossrble
to determme the composttron and the preferential
onentation correspondmg to these spots
3 3. EIectrochemlcaI propertles
The electrochemmal properties of the oxide films
are affected by their growth mode For the poten-
trostatrc i%lm,that presents a homogeneous colour m
optrcal mmroscopy, the few copper nuclei obtained
after a potentiostatic pulse of 15 s at + 56 mV vs she,
are randomly drspersed (see Fig 4a and b) On the
contrary, for the galvanostatrc and the combined
film, the copper nucler mrhally grow exactly on top
of some of the dark blue spots observed by optrcal
nucroscopy in the pale blue grams (see Fig 4c and
d) After a long (20s) potentlostatrc pulse, all the
dark blue spots together wrth the dark brown spots
observed m the yellow grams have served as centres
for the copper nucleatron (see Frg 5a and b)
The drfference between the combined hlms and the
galvanostatrc film rs lymg m the densrty of dark blue
spots and then m the density of copper nuclei This
mrcroscoprc effect IS confirmed by the macroscoprc
current transrents observed durmg these poten-
tmstatrc pulses (see Fig 6) Starting wrth nearly the
same current density, the decreasmg order of the
final current transient mtensrty 1s the galvanostatrc
film, the combined film and the potentrostatrc film
3 4 Semrconduchng propertzes
The Mott-Schottky plots are presented m hg 7,
for the three growth modes
The galvanostatic and the combmed films present
nearly the same flat band potential ( f 80 & 10 mV
vs she), the same slope m the Mott-Schottky plots
and a small linear Mott-Schottky regron On the
contrary, the potentrostatrc film presents a large
linear regron, a smaller slope and a more anodrc flat
band potential (+ 130 + 10 mV vs she) than the gal-
vanostatic film
1285
4. DISCUSSION
The influence of the growth mode on the structure
and the proper&s of thin trtamum ano&c oxrde
films 1s complex Mrcrocrystalhne structures, very
srmrlar to those reported for galvanostatrc films by
Shmuzu et al [28], are observed The mam mfluence
of the growth mode seems to be the spahal Qstribu-
non and the onentatron of these mrcrocrystals
For the potentrostatrc film, numerous randomly
oriented and homogeneously drstnbuted mmro-
crystals are observed They do not act as preferential
electronic or iomc conductmg channels and the film
is very resistrve for copper nucleation
For the galvanostatrc and combined fihns, then
mmrocrystalhmty depends on the orientation of the
underlymg trtanmm crystals Specral features corre-
spondmg to clusters contammg a small number of
hrghly or-rented mmrocrystals are observed These
clusters act as preferentml conductmg channels and
copper nucleates on top of these clusters The con-
stant potential mamtamed for 1 mm m the combined
growth mode, do not change the structure of the
anodtc film but seems to mhrbrt the nucleatmg
action of some of these clusters
The composrhons of the different regrons of the
anodrc films are htamum droxrde but then allotropic
forms (anatase or ruttle)‘are sttll a problem to be
solved wtth htgh resolutron transmrsston electron
microscopy.
The flat band potent& of the different oxrde films
are in agreement with prevrously reported
values[29-32-J The srmrlar structure of the galvano-
static and the combined films correspond to slmrlar
semtconductmg behavrour and Mott-Schottsky
plots
Taking into account the hmrtmg values, observed
m the hterature[ll, 30, 33-351, for the relative per-
mrttrvlty of the titanium anodrc oxide films (E = 10
and 100), rt IS possrble to e&mate the donor den-
sities m the films These values are m agreement wrth
literature data The donor densrtres (for E = 10) of
Before copper nucleation After cower nucleation

Fig 4 Optical mwroscoples of the tltamum anodlc oxide films before ((a) and (c)) and after ((b) and (d))
copper electrodeposltlon durmg 15 s ((a) and (b) potentlostatlc oxide film, (c) and (d) galvanostatlc oxide
film)
Influence of the anodmng procedure 1287
1288 J -L DELPLANCKE
Combmcd
Galvanostatw
I I I I I I I I
0 2 4 6 8 10 12 14
Time (s)
Rg 6 Current transients observed dunng the copper
nucleation on the anodlc oxide film (+ 56mV vs she dunng
15s)
the galvanostatlc and the combined films
(5 6 x 10”) are about tHrlce the density of the poten-
tiostatic film (2 2 x 1020)
A tentative quahtatlve explanation could be the
followmg During potentlostatlc anodlzatlon, the
current density at which the mltlal oxide film IS
growmg IS only limited by the avadable power of the
power source In most cases, the mltlal current
density 1s very high Microcrystals are formed but
their growth IS so fast that they are randomly onent-
ed They form a thick insulating oxide film On the
contrary, the galvanostatlc and the combined films
are grown at a constant current density and for some
orientations of the underlying titanium crystals, clus-
ters of oriented oxide rmcrocrystals are formed
These clusters act as preferential channels for the
current flow during cathodic polarlzatlon
According to Leltner et al [36], the donor density,
m the titanium anodlc oxide films, could be related
to point defects like oxygen vacancies A linear
relationship for the donor density vs the reciprocal
square thickness of the oxide film IS observed[37]
Taking mto account the Auger profiles and the
higher thickness of the potentlostatlc film, the more
defective character of the galvanostatlc and the com-
bined films could be explained This seems also to be
confirmed by the smaller linearity of the Mott-
Schottky plots for these two films This non-hneanty
could be related to the presence of multiple donor
levels m the oxide films[38]
015-
E (mV/ssc)
Rg 7 Senuconductmg properties and Mott-Schottky
plots of the titanium anodic onde films (a) potentiostatic,
(b) galvanostatic, (c) combined growth mode
et al
5. CONCLUSIONS
The growth mode of anodlc oxide films on tlta-
mum has a considerable mfluence on the composl-
tlon and the properties of these films From a
macroscopic point of view, whatever the growth
mode, films grown at SOV are crystalhzed but the
mlcroscoplc orientation of the mlcrocrystals depends
on the anodlnng condltlons For galvanostatlc and
I combined films, preferential conducting channels are
16 observed These channels modify the electrochemical
and semlconductmg propertles of the anodlc films
Acknowledgements-The authors are Indebted to the
National Fund for Snentdic Research of Belgmm, the
Conumssanat GenCral aux Relations Internatlonales de la
Communautt FranGzuse de Belgque and the Service cul-
turel et sclentifique de I’Ambassade de France for their
financial support
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