Passivation of Metals and Semiconductors, and Properties of Thin Oxide Layers

P. Marcus and V. Maurice (Editors)

© 2006 Elsevier B.V. All rights reserved. 179

Anodization of Ti: Formation of Self-Organized

Titanium Oxide Nanotube-Layers

p. Schmukf *, H. Tsuchiya^ L. Taveira^ K. Sirotna' and J. M. Macak^

^ University ofErlangen Nuremberg,

Dept. of Materials Science, LKO, Martensstr. 7, 91058 Erlangen, Germany
* on leave from: UFRGS - Universidade Federal do Rio Grande do Sul
Av. Osvaldo Aranha 99, 90035-190-Porto Alegre, Brasil
"" on leave from: Institute of Chemical Technology Prague,
Dept. of Power Engineering, CZ-16628 Prague, Czech Republic

Abstract - The work reports on the electrochemical fabrication of layers of self-

organized high aspect ratio titanium oxide nanotubes achieved by an optimized and
controlled anodization of Ti in fluoride containing solutions. In general, the morphology
and the structure of porous layers are affected strongly by the electrochemical
parameters used. Under optimized conditions self-organized relatively highly ordered
nanotubes with a length between some 100 nm and several |im are formed consisting of
arrays with single tube diameter between 10 and 100 nm and a tube wall of approx. 10
nm thickness. The work discusses factors of the electrochemical pore formation process
and key electrochemical factors that lead to self-organization.

Keywords : self-organization, porous titanium oxide, tubular structure, electrochemical

anodization

1. Introduction

Self-organized nanostructures of different metals or semiconductors have

received considerable attention due to the anticipated high technological
potential of these materials. For a range of metals such as Al [1-4], Ti [5-14], Zr
[15-17], Nb [18], W [19-20], Ta [21, 22], Hf [23] it has recently been found that
self-organized porous structures can be formed under optimized electrochemical
treatments. These nanoarchitectural oxide films can have very specific
180 P. Schmuki et al.

functional properties. For example, titanium oxide (TiOi) is a promising

material because of gas sensing capabilities, self-cleaning ability, and its use in
solar cells.
Nanoporous TiOi has been formed by electrochemical anodization of Ti in acid
electrolytes containing small amounts of hydrofluoric acid (HF) [5-7]. A
drawback of acidic HF-based electrolytes is that typically porous Ti02 layers
have been grown only up to thicknesses of about 500 nm, unlike Al, Hf or Zr
where porous films with thicknesses of several ten micrometers can be
obtained. Recently we obtained high aspect ratio self-organized porous Ti02
structures with thickness higher than 2 |Lim by anodization in buffered neutral
electrolytes containing NaF and NH4F instead of HF [8,9]. Thus, by exploiting
the decrease of the chemical etching rate of Ti02 in these neutral solutions and
establishing a pH gradient by adjusting the electrochemical conditions high
aspect ratio TiOi nanotubes can be grown.
The present work discusses various aspects of the pore formation process and
several critical factors affecting the pore - or nanotube - morphology.

2. Experimental

For electrochemical experiments, Ti foils (from Goodfellow, England) of 0.1

mm thickness and purity of 99,6% were used. Prior to anodization, the samples
were degreased in an ultrasonic bath in acetone, isopropanol and methanol,
followed by a deionized water rinse and then dried in a nitrogen stream.
The samples were contacted by a Cu plate and then pressed against an 0-ring in
an electrochemical cell, leaving 1 cm^ exposed to the electrolyte. The
electrochemical measurements were carried out in a classical three-electrode
configuration with a Ag/AgCl (1 M KCl) electrode as a reference electrode and
a platinum grid as a counter-electrode. The Ti samples were anodized using a
high-voltage potentiostat Jaissle IMP 88 interfaced to a computer. The
electrolytes were various acids and salts with additions of small amounts of HF
and NH4F (0.05 - 5 wt.%). The experiments were performed at room
temperature under aerated non-stirred conditions. All solutions were prepared
from chemical reagents of high purity.
For anodization, the potential was typically continuously increased from the
open-circuit potential (OCP) to an end potential with several scan rates and then
held at the end potential for different times. For surface characterization, the
specimens were rinsed with deionized water and dried with nitrogen.
Scanning electron microscope images were taken for the morphological
characterization of the porous titanium oxide using a Hitachi SEM FE 4800.
Direct SEM cross-sectional thickness measurements were carried out on
mechanically bent samples, where cracking and a partial lift-off of the porous
layer occured.
Anodization ofTi: Formation of Self-Organized Titanium Oxide Nanotube-Layers 181

3. Results and Discussion

In general, the morphology (and the thickness) of the anodic oxide layers
formed on Ti strongly depends on the electrochemical parameters such as the
applied potential, the time of anodization, or the sweep rate of the potential
ramp. Additionally, the HF-concentration in the electrolyte must be optimized
to achieve self-ordered pore growth. Anodization in solutions with a low HF-
concentration, for instance <0.05 wt.% HF in 1 M H2SO4 solution, yields large
nonregular pores. On the other hand, anodization in solutions containing > 0.5
wt.% HF leads to uniform etching of the surface (electropolishing).

3.1. Initiation of porous layers

A feature common to all porosification experiments is that establishing the final

steady state of the self-organized etching process requires an induction time.
Figure la shows schematic current-time transients for anodization of Ti at the
"right" voltage in an electrolyte e.g. H2SO4 in absence and in presence of the
"right" amount of fluoride. In pure background electrolyte, the typical
exponential current decay is observed due to the growth of a compact oxide
layer. For electrolytes containing fluorides, clear deviations from the behavior
are observed. In this case, after an initial exponential decay (phase I) the current
increases again (phase II) with a time lag that is shorter, the higher the fluoride
concentration. Then, the current reaches quasi-steady state (phase III). This
steady state current increases with increasing fluoride concentration.
This type of current-time curve has been previously reported for self-organized
pore formation for other materials, as well [24]. Typically, such a current
behavior has been ascribed to different stages in the pore formation process, as
schematically illustrated in Fig. lb. In the first stage, a barrier oxide is formed,
leading to a current decay (a). In the next stage, the surface is locally activated
and pores start randomly growing (b). Due to pore growth, the active area
increases and the current increases. After some time, many pores have initiated
and a tree-like growth takes place. Therefore, the individual pores start
interfering with each other, and start competing for the available current. This
leads under optimized condition to a situation where the pores equally share the
available current, and self-ordering under steady-state conditions is established
(c).
Indeed, direct SEM cross-sectional observation take for each sample at the three
phases delineated in Fig. 1 confirms the above description regarding nanotube
formation. Fig. 2 shows samples removed fi'om the electrolyte after different
times - shown is the evolution of the morphology of the porous titanium oxide
in 1 M (NH4)2S04 + 0.5 wt. % NH4F. Immediately after the sweep from the
OCP to 20 V, a thin and rough oxide film (~ 50 nm) covers all the surface of the
titanium (Fig. 2a). The results from XPS measurements show that the film at
this stage is composed of Ti, O and some traces of F. The XPS data suggest that
182 P. Schmuki et al

the film is composed of an inner layer of TiOi and a outer layer of Ti(0H)4.
This film is essentialy the high-field passive layer - the thickness very well
corresponds to a growth factor of 2.5 nm / V. At approximately 3 min, first
signs of localized attack become apparent with the FE-SEM; breakdown sites
that are randomly distributed over the film surface and round shaped holes in
the substrate can be observed. Then, the current increases due to the growth of
the pores. At this point, the SEM image reveals that underneath the relatively
compact top oxide film some pore structures become visible. The porous oxide
film shows in the cross-section a thickness of 200 to 300 nm and a relatively
regular but worm-like structure (Fig. 2b). After 30 min from the start of the
polarization, there are areas of porous structure visible but still there are patches
of the top compact oxide film visible. With increasing anodization time the
current drops further while the porous oxide film thicknesses establishes at 500-
800 nm (Fig. 2c). Anodization for longer times leads to a further establishment
of the homogenous self-organized porous structure.

3.2. Thickness and morphology of the porous layers

The thickness of the porous layers was determined from SEM cross-sections of
mechanically fractioned samples. For anodization in 1 M H2SO4 + 0.15 wt.%
HF the thickness of the porous layer was found to first steeply increases from
about 47 nm at 20 minutes to 540 nm after 10 hours. This is followed by a
steady state with a plateau of thickness values at approximately 580 nm.
The fact that, both the current and the porous layer thickness reach a limiting
value after a certain polarization time can be explained by a steady-state
situation. Both, pore growth at the inner interface and dissolution of the oxide
layer at the outer interface take place. Steady state is established when the pore
growth rate at the inner interface is identical to the dissolution rate of the oxide
film at the outer interface.
This limiting porous oxide layer thickness can be overcome by the
electrochemical conditions [9]. That is, higher thickness of the porous layer can
be obtained, if the anodization treatment is carried out in less aggressive
electrolytes. One explains the fact that the hydrolysis reaction during
anodizafion leads to acidification of the pore tips (similar to pitting corrosion).
This acidification accelerates the chemical TiOi dissolution exactly there, where
it is desired: at the pore tip (while the rest of the porous structure remains
relatively stable due to the more alkaline pH of the background electrolyte) -
for more details see Ref. [9]. Fig. 3 and Fig. 4 show top views and cross-
sectional SEM images of a range of porous Ti02 layers produced in different
electrolytes. Clearly the thickness of the oxide layer depends on the aggressivity
of the electrolyte and is in line with the idea that the pore growth mechanism is
controlled by competing film growth and dissolution.
Another crucial factor that was found in various electrolytes to affect the pore
morphology is the potential scan rate. This is also well in line with the approach
Anodization ofTi: Formation of Self-Organized Titanium Oxide Nanotube-Layers 183

that local acidification crucially determines the morphology. The higher the
scan rate, the higher the current density and therefore the lower the pH at the
pore tip and the higher the H^ flux from the tip to the pore mouth [9]. Hence it
is understandable that only optimized scan rates (and therefore pH - profiles
within the pore) can produce high aspect ratio tubular structures.

3.3. Electrolytes and pore dimensions

The results in Fig. 3 and 4 clearly show that the morphology of the single pores
and the pore dimensions that are the pore diameter, the pore spacing, the pore
lenght and the occurance of a rippled side-wall strongly depend on the
electrolyte used.
Fig. 3 and Fig. 4 show pores produced using H^SO^, (NH,)2S04, CH3COOH and
(NH4)H2P04 electrolytes. The pore diameter varies from a 15 nm in CH3COOH
to approx. 100 nm in (NH4)2S04. The pore lenght can be varied from approx.
200 nm to about 5 |Lim.

4. Conclusions

Self-organized porous Ti02 layers can be electrochemically prepared by

anodization in electrolytes containing small amounts of F" species.
The self-organized pore growth takes place as a steady-state process, as a
competition of activation and passivation reactions. Hence, a limiting thickness
of the porous oxide layer is established.
By optimizing the anodization parameters, self-organized porous Ti02 layers
with a comparably high degree of order and various dimensions and aspect
ratios can be achieved.

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barrier layer (TiO,/Ti(OH),)

Ti (a)
barrier layer
\ "worm" structure

0)
Ti (b)
o barrier layer ^ . -
\ -' patches of
\ porous structure

Time 24h Ti (c)

Fig la) Schematic polarization curve and stages Fig.lb) Schematic representation of the
(I,II,III) of pore formation. stages (I=a, II=b, III==c) of self-
organized pore formation.
Anodization ofTi: Formation of Self-Organized Titanium Oxide Nanotube-Layers 185

Fig. 2. SEM top-view and cross-section

images show the evolution of porous titanium
oxide morphology after anodizing for (a) 0 - 1
min; (b) 6 min; (c) 20 min; in 1 M (NH4)2S04
+ 0.5 %wt. NH4F electrolyte at 20 V (after a
potential sweep from open-circuit potential to
20 V with weep rate of 1 V s"^).

Fig. 3. Influence of the electrolyte on tube diameter [8-10, 12]. Top-view images of the porous
titanium oxides prepared in (a) CH3COOH/NH4F, (b) (NH4)H2P04/NH4F, (c) H2SO4/HF and (d)
(NH4)2S04/NH4F.
186 P. Schmuki et al.

Ammonium buffe^ Phosphate buffer

t = 700 t=1.4
, ''^ ,

t = 4.1 pm

•#^« J:,; X'. 'i '•:': \ '.

- l i r M v ^ ' . ; ! , - f-'--.. V ;'!•-'• I'll
:/'^^lt^'r';

Fig 4: Influence of the electrolyte on tube length [8-10, 12]: (for different electrochemical
conditions)