Journal of The Electrochemical Society, 157 共6兲 K125-K130 共2010兲 K125

0013-4651/2010/157共6兲/K125/6/$28.00 © The Electrochemical Society

Evaluation of Fluorine Ion Concentration in TiO2 NT

Anodization Process
Chien-Chon Chena and Sheng-Jen Hsiehb,z
a
Department of Energy and Resources, National United University, Lienda, Miaoli 36003, Taiwan
b
Department of Engineering Technology and Department of Mechanical Engineering, Texas A&M University,
College Station, Texas 77843-3367, USA

Studies have shown that fluorine ions play a significant role in the initiation and growth of TiO2 nanotubes. As fluorine is doped
in titanium nanotubes 共TiO2 NTs兲, fluoride gases form during TiO2 NT anodization. The concentration of fluorine in an electrolyte
decreases as the anodization period increases. Maintaining a constant concentration of fluorine levels is a challenging task. In this
paper, we discuss and calculate the quantity of fluorine reduced in an electrolyte given various electrolyte temperatures, sample
sizes, and anodization time effects. According to thermodynamic calculations, F, FO, and FO2 have relatively low vapor pressures
but HF, H2F2, H3F3, H4F4, H5F5, H6F6, and H7F7 have relatively high vapor pressures during anodization. The effects of fluorine
contained in TiO2 NT 共12.2 wt %兲 and vaporized from the electrolyte can cause the fluorine concentration in the electrolyte to
decrease.
© 2010 The Electrochemical Society. 关DOI: 10.1149/1.3374640兴 All rights reserved.

Manuscript submitted December 1, 2009; revised manuscript received February 15, 2010. Published April 22, 2010.

The first TiO2 nanotube 共NT兲 arrays were formed by Zwilling et
al.1 More recently, as shown in Table I, short TiO2 NTs have been
made and studied in great detail.2-9 Cai et al.’s10 and Grimes’11
groups fabricated TiO2 NTs by the anodization process, and tube
lengths were controlled by varying the amount of fluoride ions in the
electrolyte. For example, an aqueous HF-based electrolyte grew
0.5 ␮m long NTs, an aqueous NaF- or KF-based electrolyte grew
6.8 ␮m long NTs,10 and a nonaqueous F-ion-based electrolyte grew
134 ␮m NTs.12 Mor et al.13 fabricated TiO2 NTs for use in a pho-
tocleavage reaction, dye-sensitized solar cells 共DSSC兲, hydrogen
sensing, and self-cleaning sensor studies.
With regard to DSSC power conversion efficiency, the freestand-
ing TiO2 NT film has better performance than the TiO2 NT film on
a Ti substrate due to the front side being illuminable and due to the
absence of a barrier layer between the NT membrane and the Ti
substrate. Mor et al.14 and Paulose et al.15 fabricated a TiO2 NT film
on fluorine-doped tin oxide glass using sputter and anodization pro-
cesses. Also, Albu et al.,16 Chen et al.,17 and Park et al.18 described
a process by which NT array films can be transformed into free-
standing membranes.
Anodization of titanium foil in F− and minimizing water content
in a nonaqueous organic polar electrolyte form closely packed, ver-
tically aligned NTs. This electrochemical processes may be de-
scribed as follows19-21
Ti → Ti4+ + 4e−
H2O → 2H+ + O2−
the electrolyte through ion migration 共Reactions 3 and 4兲. Fluorine
ions etch TiO2, forming 关TiF6兴2−, and then combine with H2O to
form 关TiF6−n共OH兲n兴2− 共Reactions 5 and 6兲. Because the fluorine
ions are doped in TiO2 but do not form a compound, Reaction 6 can
be rewritten as Reaction 7. Finally, 关Ti共OH兲6兴2− reacts to 2H+ form-
ing TiO2 NTs 共Reaction 8兲.
Studies have shown that fluorine ions play a significant role in
the initiation and growth of TiO2 NTs. The fluorine ions nucleate
titanium metal, generate interconnected pores, and allow current to
flow within the oxide film. The dispersed pores align in the direction
of the applied electric field to generate an array of tubes.22-24
He et al.25 studied the influence of fluorine on the structure and
photocatalytic activity of TiO2 film in a tungstate electrolyte. Re-
sults suggest that the porosity, element content, and phase composi-
tion of TiO2 films are affected by fluorine ion concentration in an
electrolyte. The number of pores, the content of tungsten, and the
content of the anatase phase all increase when fluorine ions were
added to the electrolyte.
Grimes reported that relatively long TiO2 NTs were fabricated
after a period of anodization when Ti was in an organic solvent, and
solutes of H2O and NH4F were controlled in 2 vol % and 0.25–0.8
wt %.12,13 In anodization, good quality TiO2 NT can be obtained by
carefully controlling fluorine concentrations. However, fluorine va-
por gas has been observed during anodization, and fluorine is de-
关1兴 tected in the TiO2 NT. In this paper, we calculate the fluorine con-
sumption rate during a period of anodization based on
electrochemical and thermodynamic data.
关2兴

Ti4+ + 2O2− → TiO2 关3兴 Experimental

Ti4+ + 2H2O → 4H+ + TiO2 关4兴 An ordered channel array of anodic titanium oxide was fabri-
cated by anodizing titanium 共Ti兲 foil 共Aldrich, 99.7%兲. Ti foil
6F− + TiO2 + 4H+ → 关TiF6兴2− + 2H2O 关5兴 was first fabricated using electropolishing 共EP兲. The EP conditions
involved a platinum sheet as a cathode, titanium plate as an
关TiF6兴2− + nH2O → 关TiF6−n共OH兲n兴2− + nH+ + nF− 关6兴 anode, 5 vol % perchloric acid 共HClO4兲 + 53 vol % ethylene
glycol monobutylether 共HOCH2CH2OC4H9兲 + 42 vol % methanol
关TiF6−n共OH兲n兴2− + 共6 − n兲H2O → 关Ti共OH兲6兴2− + 共6 − n兲H+ 共CH3OH兲 as an electrolyte at 15°C, 52 V for 1 min followed by 28
+ 共6 − n兲F− 关7兴 V for 13 min at a constant stirring rate of 200 rpm. After EP, the
sample was then etched in 5 vol % HF for 5 min to add an additional
关Ti共OH兲6兴2− + 2H+ → TiO2 + 4H2O 关8兴 layer of anodic film on the Ti substrate. TiO2 NT growth was
achieved using electrolyte solutions 共pH 6.8兲 of 0.15, 0.25, and 0.5
During anodization, oxidation reactions occur at the metal/ wt % ammonium fluoride 共NH4F,99.9%兲 + 2 wt % H2O in ethyl-
electrolyte. Reaction 1 is formed, and the water in the electrolyte is ene glycol 关C2H4共OH兲2兴 solvent with anodization at a constant volt-
decomposed 共Reaction 2兲. TiO2 then forms between the metal and age of 60 V for periods ranging from 0.5 to 12 h. The micromor-
phology and composition of the TiO2 NT were determined by using
a scanning electron microscope 共SEM, JEOL 6500兲 and energy-
z
E-mail: hsieh@tamu.edu dispersive spectroscopy 共EDS兲. The TiO2 NT growth rate and the

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K126 Journal of The Electrochemical Society, 157 共6兲 K125-K130 共2010兲

Table I. Fabrication parameters for short TiO2 NT.

Voltage Time Temperature Pore size Length

Electrolyte 共V兲 共h兲 共°C兲 共nm兲 共␮m兲 Annealing Phase Reference

1% HF 20 0.5 22 100 ⬍1 None Amorphous 5

KF 共0.1 M兲 + HNaSO4 共1 M兲 + C6H5O7Na3
+ 2H2O 共0.2 M兲, pH 5 25 17 22 110 6 600°C, 17 h Anatase 6
HF 共1 vol %兲 20 0.75 22 76 0.4 280°C, 3 h Anatase 7
HF 共0.5 vol %兲 + H3PO4 共1 M兲 20 12 22 100 1.1 450°C, 3 h Anatase 8
HN4H2PO4 共1 M兲 + NH4F 共0.5 wt %兲 15 — 22 70 3 450°C, 3 h Anatase 9
HF 共0.5 vol %兲 20 0.3 18 60 0.25 None Amorphous 10
H2SO4 共10 vol %兲 + HF 共1.2 vol %兲 20 0.025 25 100 0.17 None Amorphous 11
HN4SO4 共1 M兲 + NH4F 共0.5 wt %兲 20 2 22 100 2 450°C, 3 h Anatase 12

F−, FxOy共g兲, and HxFy共g兲 activities during anodization were evalu-
ated using thermochemical data and thermodynamic calculations.
Results and Discussion
To calculate the rate of TiO2 NT growth on the substrate, we
used NH4F electrolyte in ethylene glycol at three concentrations to
anodize Ti foil for various amounts of time. Figures 1-3 show side
views of TiO2 NT lengths as a function of time period of anodiza-
tion; the length increases with increasing duration of anodization
and F− concentration. Figure 4 shows thickness curves of TiO2 NT
with anodization times when the TiO2 NT grows in electrolytes
containing 0.15, 0.25, and 0.5 wt % NH4F at a constant voltage of
60 V. The NT growth rates in electrolytes containing 0.15, 0.25, and
0.5 wt % NH4F are about 1.8, 2.6, and 4.8 ␮m h−1, respectively.
Figure 5 shows the SEM images of the TiO2 NT microstructures
and structure, including 共a兲 the top view of TiO2 NTs with a 120 nm
pore diameter, a 150 ⫾ 5 nm pore distance, a 20 ⫾ 5 nm pore wall

Figure 1. Side view SEM images of TiO2 NT film showing various NT Figure 2. 共Color online兲 Side view SEM images of TiO2 NT film showing
lengths 共L兲 after anodization for t/h = 共a兲 1, 共b兲 2, 共c兲 3, 共d兲 4, 共e兲 6, 共f兲 9, 共g兲 various NT lengths 共L兲 after anodization for t/h = 共a兲 0.5, 共b兲 1, 共c兲 2, 共d兲 4,
10, and 共h兲 12; electrolyte: 0.15 wt % NH4F. 共e兲 5, 共f兲 6, 共g兲 8, and 共h兲 10; electrolyte: 0.25 wt % NH4F.

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 Journal of The Electrochemical Society, 157 共6兲 K125-K130 共2010兲
Figure 3. 共Color online兲 Side view SEM images of TiO2 NT film showing
various NT lengths 共L兲 after anodization for t/h = 共a兲 0.5, 共b兲 1, 共c兲 2, 共d兲 3,
共e兲 4, 共f兲 5, 共g兲 6, and 共h兲 8; electrolyte: 0.50 wt % NH4F.
thickness, and a 8 ⫻ 109 tubes/cm2 pore density, 共b兲 the lower view
of TiO2 NT with 80 nm pore diameter, 共c兲 the barrier layer on the
bottom of the tubes, 共d兲 the 95 nm pore diameter near the top of the
tubes, 共e兲 the 60 nm pore diameter near the bottom of the tubes, and
Figure 4. 共Color online兲 Thickness curves of TiO2 NT with anodization time
when the TiO2 NTs are grown in an electrolyte with various NH4F concen-
trations.
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K127
Figure 5. SEM images show TiO2 NT microstructures. 共a兲 Top view of TiO2
NTs with 120 nm pore diameter, 共b兲 lower view of TiO2 NTs with 80 nm
pore diameter, 共c兲 barrier layer on the bottom of the tubes, 共d兲 95 nm pores
diameter near the top tube, 共e兲 60 nm pore diameter near the bottom tube, 共f兲
schematic diagram of TiO2 NT with radii of R1 共top pore兲, R2 共bottom pore兲,
and R3 共outer column兲, and length 共L兲 structure, and 共f兲 NT length with
surface area curve.
共e兲 a schematic diagram of TiO2 NT with radii R1 共top pore兲, R2
共bottom pore兲, and R3 共outer column兲 and length 共L兲 structure.
Based on Fig. 5a, b and d, TiO2 NTs connect to one another within
a localized area. Therefore, the electrolyte should be able to perme-
ate into the tube interface, and the active surface area should include
both the outer 共Ao兲 and inner 共Ai兲 tube surface areas. As shown in
Fig. 5f, the TiO2 NT surface area can be represented by 共Ao + Ai兲
⫻ P, where Ao is the outer tube surface area, Ai is the inner tube
surface area, and P is the tube density. Furthermore, Ao = 2␲R3L
and Ai = ␲共R1L + R2L + R2R2兲. Therefore, when R1 = 120 nm,
R2 = 50 nm, and P = 8 ⫻ 109 tubes/cm2, a curve of TiO2 NT sur-
face areas for various NT lengths can be drawn. In Fig. 5f, TiO2 NT
with 60 ␮m NT length has a surface area of 3580 cm2 on a 1 cm2
substrate. In other words, in a 1 cm3 sample of a TiO2 NT structure,
the total surface area of all the NTs is 596,600 cm2, and in a com-
pact cube with a surface area of 6 cm2, the total surface area for all
the NTs increases by a factor of 99,433. The weight of the TiO2 NT
can be calculated as 共Vo − Vi + Vb兲 ⫻ ␳, where Vo is the outer tube
volume 共column兲, Vi is the inner tube volume 共cone兲, Vb is the
volume of the barrier layer, and ␳ is the TiO2 density
共4.32 g cm−3兲. Therefore, the weight of each TiO2 NT can be cal-
culated as follows
weightTiO2 NT = 共4.32 g cm−3兲 ⫻ 共␲R21 ⫻ L兲 − 关 31 ␲R21共L + t兲
− 3 ␲R22t兴
1
关9兴
where t is the barrier layer thickness 共100 nm兲. Therefore, the
weight of each TiO2 NT and the total TiO2 NTs with various NT
lengths can be calculated. For example, Fig. 6 shows a curve of
TiO2 NTs with various NT lengths, 共a兲 the weight of a single TiO2
K128 Journal of The Electrochemical Society, 157 共6兲 K125-K130 共2010兲

Figure 6. 共Color online兲 Curves of TiO2 NT weight with various NT lengths,

共a兲 weight of single TiO2 NT at various NT lengths, 共b兲 total TiO2 NTs
weight with various NT lengths and 10, 50, and 100 cm2 sample sizes.

NT, and 共b兲 the weight of TiO2 NT samples of 10, 50, and 100 cm2.
Albu et al. reported that the atomic composition of TiO2 NT is
23.9% Ti, 53.4% O, 13.7% F, 0.9% N, 6.8% C, and 1.1% S, as
analyzed by X-ray photelectron spectroscopy.16 Because the atomic
weights 共amu兲 of Ti, O, F, N, C, and S are 47.7, 16, 19,14, 12, and
32, respectively, the TiO2 NT composition by weight can be calcu-
lated as 47.8% Ti, 35.8% O, 10.9% F, 0.5% N, 3.4% C, and 1.5% S.
In our measurements, the basic TiO2 NT composition, as detected
by SEM and EDS, of 12.2 wt % fluorine concentration was close to
Grimes’s report of 10.9 wt %. Figure 7 shows 共a兲 the SEM image
and 共b兲 the EDS of TiO2 NTs composed of Ti, O, and F of 37.9,
48.1, and 12.2 wt % when Ti foil was anodized in a solvent consist-
ing of 0.5 wt % NH4F + 2 wt % H2O + C2H4共OH兲2. The F ions
are doped from an electrolyte containing fluorine. For example,
there is 1.4 g fluorine in 0.073 M 共mol/L兲 or 0.25 wt % NH4F of 1
L electrolyte. Using Fig. 6 and 7b, the weight of fluorine in TiO2
NTs can be evaluated. For example, a 100 cm2 sample size with
30 ␮m TiO2 NT film on the surface contains 0.0947 g fluorine
doping in the TiO2 NTs wall. The evaluation of fluorine weight in
TiO2 NT with varying surface areas is shown in Fig. 7c. Because the
Ti foil is ionized, NH4F and H2O are decomposed, and air is dis-
solved in the electrolyte; the elements Ti, F, C, H, O, and N can be
detected in TiO2 NT. From thermodynamic principles, we know that
Ti, O, and H can form TiO, Ti共OH兲3, Ti共OH兲4, or TiO3·H2O. F, O,
and H can form F, FO, and FO2 and HF, H2F2, H3F3, H4F4, H5F5,
Figure 7. 共Color online兲 共a兲 SEM image, 共b兲 EDS of TiO2 NT composition
including 37.9 wt % Ti, 48.1 wt % O, and 12.2 wt % F, and 共c兲 fluorine
weight in TiO2 NTs, which increases as NT length increases with 10, 50, and
100 cm2 sample sizes.
and H6F6 during the anodization process. In short, the anodization
process causes the F, C, H, and O concentrations in the electrolyte to
decrease.
Figure 8 shows Pourbaix diagrams of the 共a兲 Ti–H2O and 共b兲
F–H2O reaction systems. In a Ti–H2O system, immersing titanium
in electrolyte generates various substances. These include nine sol-
ids 关titanium 共Ti兲, titanium monoxide 共TiO兲, hypotitanous hydroxide
共TiO·H2O or Ti共OH兲2兲, titanium sesquioxide 共Ti2O3兲, titanium hy-
droxide 共Ti2O3·H2O or Ti共OH兲3兲, blue oxide 共Ti3O5兲, titanium di-
oxide or rutile 共TiO2兲, hydrated dioxide 共TiO2·H2O or Ti共OH兲4兲,
and hydrated peroxide 共TiO3·2H2O兲兴 and seven dissolved sub-
stances 关hypotitanous: ions 共Ti+2兲, titanous ions 共Ti+3兲, titanyl ions
共TiO+2兲, titanate ions 共HTiO−3 兲, pertitanyl ions 共TiO+2
2 兲, acid perti-

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 Journal of The Electrochemical Society, 157 共6兲 K125-K130 共2010兲
Figure 8. Pourbaix diagrams of 共a兲 Ti–H2O and 共b兲 F–H2O reaction sys-
tems. In Ti–H2O diagram, Ti ions prefer forming in lower and higher pH
ranges but TiOx or Ti共OH兲x prefer forming in a medium pH range. In the
F–H2O diagram, HF, F−, and F2O共g兲 are present in the lower potential and
pH value, lower potential but higher pH value, and higher potential condi-
tions.
26
tanate ions 共HTiO−4 兲, and pertitanate ions 共TiO−24 兲兴. A complex
reaction occurs among the 16 forms of titanium in an aqueous solu-
tion. The Pourbaix diagram is useful for simplifying the complex
reaction. The Ti–H2O Pourbaix diagram shows that Ti ions prefer
forming in lower and higher pH ranges, but TiOx and Ti共OH兲x pre-
fer forming in a medium pH range. The Ti dissolved in the solution
when the pH of the electrolyte was under 2.5, and the standard
electrode potential exceeded ⫺1.81 V 共standard hydrogen elec-
trode兲. Applying a constant voltage of 60 V to the titanium effec-
tively dissolved Ti according to Ti → Ti+2 → TiO+2. TiO+2 com-
bined easily with OH− to form TiO2·H2O or Ti共OH兲4 when the pH
of the solution of TiO+2 was increased to yield strongly acidic con-
ditions.
In the F–H2O Pourbaix diagram, HF共g兲, F−, and F2O共g兲 are
present in the lower potential and pH value, lower potential but
higher pH value, and higher potential conditions. During anodiza-
tion, F2O共g兲 and HF共g兲 were formed in the electrolyte22 and F−
doping to 共TiOH兲4, and gases F共g兲, FO共g兲, FO2共g兲, HF共g兲, H2F2共g兲,
H3F3共g兲, H4F4共g兲, H5F5共g兲, H6F6共g兲, and H7F7共g兲 were
produced.27,28 Thus, the concentration of F in the electrolyte de-
creased as the length of the anodization period increased. In TiO2
NT anodization, NH4F first decomposes to NH3共g兲 + HF共g兲, and
then HF共g兲 decomposes to H+ + F−. When F− forms, part 共about
12.2 wt %兲 of F− dopes in TiO2 NT 共Fig. 7b兲 and part of F− forms
F共g兲, FOx共g兲, and HxFy gases.
The reaction equilibrium between F− and F共g兲 can be illustrated
as
F− → F共g兲 + e− 关10兴
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K129
Figure 9. 共Color online兲 Curves of 共a兲 F共g兲, FxOy共g兲, and HxF共g兲 vapor
pressures and 共b兲 total fluorine pressure with various fluorine activation co-
efficients in a 25°C electrolyte.
The equilibrium constant K is illustrated as Eq. 11, where PF共g兲 is the
pressure of F共g兲, and aF− is the activity of F−
P F共g兲
K= 关11兴
a F−
According to dilute solution characteristics,29 aF− can be illustrated
as
aF− = 共wt % F兲 ⫻ ␥F 关12兴
where ␥F is the activity coefficient of fluorine ions in solution.
Therefore, based on Eq. 11 and 12, the partial pressure of F共g兲 in
solution can be illustrated as
log PF共g兲 = log K + log共wt % F兲 + log ␥F 关13兴
In Fig. 9a, F, FO, and FO2 have lower vapor pressures, but HF,
H2F2, H3F3, H4F4, H5F5, H6F6, and H7F7 have higher vapor pres-
sures; furthermore, when the logarithm of the activity coefficient of
HF is less than 1.6, the HF has the highest vapor pressures in the
electrolyte, but when the activity coefficient of H3F3 is larger than
1.6, H3F3 has the highest vapor pressures in the electrolyte. Figure
9b shows the total fluorine pressure with various fluorine activity
coefficients in a 25°C electrolyte.
Assuming that the total fluorine pressure is a little higher than the
ambient pressure 共1 atm兲, the fluorine activity coefficient can be
evaluated as a = 0.021 共log a = −1.68兲 at 25°C. Furthermore,
based on the calculations from Eq. 12, the activities are 0.03, 0.05,
and 0.1 in 0.15, 0.25, and 0.50 wt % containing electrolytes at 25°C,
respectively. According to Eq. 8, the reaction can be expressed as
K130 Journal of The Electrochemical Society, 157 共6兲 K125-K130 共2010兲
Ti共s兲 + 3O2共g兲 + 8H2共g兲 → TiO2共s兲 + 4H2O共l兲 关14兴
The partial pressures of O2共g兲 and H2共g兲 in the solution can be
illustrated as
−8 1 1. V. Zwilling, M. Aucouturier, and E. Darque-Ceretti, Electrochim. Acta, 45, 921
log PO2 = 3 log PH2 − 3 log K 关15兴
27
where log K = 154 at 298 K. Therefore, the relationship between
the partial pressures of O2共g兲 and H2共g兲 is
log PO2 = − 2.67 log PH2 − 51.3 关16兴
From Eq. 14 and 16, we can see that the formation of TiO2 NT
requires little oxygen but a large quantity of hydrogen 共pressure兲 in
the electrolyte because of most of the hydrogen escapes from the
cathode during anodization.
Conclusions
Based on experimental results, TiO2 NT have open pores at the
top of the tubes, closed pores at the bottom, a compact hexagonal
column structure at the outer layers, and a hollow conical column
structure inside. We measured 0.75 g in a 100 cm2 sample size of
30 ␮m TiO2 NTs, so the density of TiO2 NT is 2.5 g cm−3, which
is less than that of bulk TiO2, which has a density of 4.32 g cm−3.
We detected 0.0947 g fluorine doping in 30 ␮m TiO2 NTs in a
100 cm2 sample size after 8 h of anodization. The fluorine con-
sumption rate is 39.4 mg cm−3 h−1. Furthermore, the fluorine was
also consumed via HF共g兲, H2F2共g兲, F3O3共g兲, F4O4共g兲, F5O5共g兲,
F6O6共g兲, and F7O7共g兲 vapor escape. The concentration of fluorine
decreases with the TiO2 NT surface area and as anodization time
increases. Based on thermodynamic calculations, the fluorine acti-
vation coefficient can be evaluated as a = 0.021 共log a = −1.68兲,
and fluorine activity can be calculated as 0.03, 0.05, and 0.1 in 0.15,
0.25, and 0.50 wt % containing electrolytes at 25°C, respectively.
The solvent of C2H4共OH兲2 and the solute of NH4F are dissolved
during anodization. Thus, because C2H4共OH兲2 has a lower dissolu-
tion rate than NH4F, adding NH4F into the solvent can maintain
electrolytes for a long period of use.
Acknowledgments
This study was partially supported by a grant from the National
Science Council of Taiwan 共98-2221-E-239-023兲.
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Texas A&M University assisted in meeting the publication costs of this
article.
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