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Electrochemical Deposition of Platinum from Aqueous Ammonium

Hexachloroplatinate Solution

Article  in  Journal of The Electrochemical Society · November 2005

DOI: 10.1149/1.2047407

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C738 Journal of The Electrochemical Society, 152 共11兲 C738-C743 共2005兲
0013-4651/2005/152共11兲/C738/6/$7.00 © The Electrochemical Society, Inc.

Electrochemical Deposition of Platinum from Aqueous

Ammonium Hexachloroplatinate Solution
John J. Whalen III,a,*,c James D. Weiland,b and Peter C. Searsona,*
a
Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218,
USA
b
Doheny Vision Research Center, University of Southern California, Los Angeles, California 90033, USA

The morphology, microstructure, and electrochemical properties of platinum thin films deposited from aqueous ammonium
hexachloroplatinate are dependent on the deposition potential. With increasing overpotential, the grain size increases and the films
exhibit stronger 共111兲 texture. Films deposited at low overpotential exhibit very small grain size and a preferred 共311兲 texture. In
addition, films deposited at −0.5 and −0.6 V are porous with very high surface areas. The electrochemical response of the films
is dependent on the morphology and microstructure.
© 2005 The Electrochemical Society. 关DOI: 10.1149/1.2047407兴 All rights reserved.

Manuscript submitted March 16, 2005; revised manuscript received June 23, 2005. Available electronically September 21, 2005.

Platinum is widely used in applications ranging from fuel cells to
biomedical implant electrodes. Its unique combination of properties
include high catalytic activity, good biocompatibility, and chemical
stability over a wide potential range. With the increased use of mi-
crofabrication techniques for the fabrication of complex three-
dimensional architectures for these and other applications, there is
an increased interest in the electrodeposition of platinum.
The electrodeposition of platinum usually proceeds through the
reduction of Pt共II兲 or Pt共IV兲 complexes with complexing ligands
such as Cl, NH3, NO2, and H2O.1 Historically, the first reports of
electrodeposition of platinum, which date back to the 1800s, were
based on acidic 关Pt共IV兲Cl6兴2− solutions.1 In acidic chloride solutions
and in the presence of Pt共0兲, the formation of 关Pt共II兲Cl4兴2− is sig-
nificant since the Pt共IV兲/Pt共II兲 equilibrium 2共PtCl4兲2− ↔ PtCl2− 6 Teflon cell with a main chamber containing a platinum mesh counter
+ Pt + 2Cl− is shifted strongly to the left. Furthermore, the substi-
tution of chloride ligands by water results in the formation of
共2−x兲−
Pt共II兲Cl4−x共H2O兲x complexes over the period of days.2 In gen-
eral, films deposited from these solutions have small grain size and
large internal stresses that lead to cracking, especially for film thick-
nesses in excess of about 1 ␮m.
Alkaline deposition solutions include tetrammineplatinum共II兲,
关Pt共II兲共NH3兲4兴2+, and dintroammineplatinum, Pt共II兲共NH3兲2共NO2兲2,
buffered to ⬃pH 10 using dilute sodium phosphate.3-7 The current
efficiency of these solutions is strongly dependent on temperature,
increasing sharply from very low values 共⬍0.1兲 to moderately high
values 共⬎0.5兲 at 60°C for Pt共II兲共NH3兲2共NO2兲2 and 90°C for
关Pt共II兲共NH3兲4兴2+. Platinum deposition has also been reported from
alkaline 关Pt共IV兲共OH兲6兴2− solution.1 Thin films can be deposited
with high deposition efficiency at elevated temperatures, although
the solutions are relatively unstable due to carbonation reactions.
In this paper, we report on the deposition of platinum thin films
from near-neutral 关Pt共IV兲Cl6兴2− solution. We show that the mor-
phology and microstructure of the films are strongly dependent on
the deposition potential. The electrochemical response of the films is
also shown to be dependent on the morphology and microstructure.
Experimental
Platinum films were deposited from solution containing 17 mM
共NH4兲2PtCl6 共Alfa Aesar兲 and 250 mM Na2HPO4 共Alfa Aesar, ACS
grade兲 at pH 7.8. Sodium hydrogen phosphate 共1.75 g兲 was first
added to distilled, deionized water 共50 mL兲 with stirring. Once dis-
solved, the ammonium hexachloroplatinate 共0.3785 g兲 was added
resulting in the formation of a transparent yellow/orange solution.
The concentration of 共NH4兲2PtCl6 is close to the solubility limit and
* Electrochemical Society Active Member.
c
Present address: Doheny Vision Research Center, University of Southern Califor-
nia, Los Angeles, CA 90033.
the solution was stirred for 24 h prior to performing experiments. In
general, reproducible results were obtained as long as the solution
was used within about 48 h of preparation. At longer times, a pale
yellow precipitate was formed.
All experiments were performed on polycrystalline gold films
共⬎150 nm thick兲 evaporated onto Si共111兲 wafers with a 4 nm chro-
mium adhesion layer. Prior to each experiment, the gold films were
immersed in acetone and rinsed sequentially in isopropanol, ethanol,
and water. Finally, the films were immersed in 5 M nitric acid and
rinsed in distilled, deionized water. Platinum foils 共Alfa Aesar, Pre-
mion 99.99%兲 were annealed in air at 700°C for 2 h, etched in
HNO3 to remove any oxide, and rinsed in distilled, deionized water.
All deposition experiments were performed in a three-electrode
electrode located parallel to the working electrode. The reference
electrode chamber was connected to the main chamber via a Luggin
capillary. The reference electrode was a Ag/AgCl共3 M NaCl兲.
All potentials are reported with respect to this reference 关Ueq
= 0.220 V vs standard hydrogen electrode 共SHE兲兴.
Platinum films were deposited at constant potential for 2 h cor-
responding to deposition charges of 3.14–10.5 C cm−2 and film
thicknesses of 30–195 ␮m. The deposition efficiency was deter-
mined from the deposition charge and the mass change, assuming an
overall four-electron reduction.
Electrodeposited platinum films were characterized by cyclic
voltammetry in 50 mM H2SO4 and by studying underpotential
deposition 共UPD兲 of copper in 50 mM H2SO4 and 1 mM CuSO4.
Experiments were performed in a sealed glass cell under nitrogen
with a platinum mesh counter electrode and a Ag/AgCl 共3 M NaCl兲
reference electrode connected to the cell via a Luggin capillary.
Voltammograms were initiated at the open circuit potential, and
swept in the positive direction, over the potential range from
−0.2 to 1.25 V. In order to compare films with different morpholo-
gies, the UPD stripping peaks were compared by first holding the
potential at 0.1 V for different times and then scanning the potential
to 0.7 V.
The crystal structure of the films was determined by X-ray dif-
fraction 共Philips X’Pert PW 3040兲 with a Cu K␣ source. The lower
limit of the grain size was estimated from the peak broadening using
the Scherrer equation:8 B = k␭/s cos ␪, where B 共radians兲 is the full
width at half-maximum 共fwhm兲 in the 2␪ scan, k is a constant
共0.94兲, ␭ is the X-ray wavelength 共0.154056 nm兲, s is the grain size,
and ␪ is the angle of the diffraction peak 共degrees兲. Note that B2
= b2 − ␤2, where b is the experimental fwhm and ␤ is the instru-
mental broadening 共0.06°兲.
X-ray photoelectron spectroscopy 共XPS兲 experiments were car-
ried out with a Phi 5100 spectrometer using the Mg K␣ 共1253.6 eV兲
radiation at a 45° takeoff angle. Following deposition, films were
rinsed in distilled water and dried in a nitrogen stream. The samples
 Journal of The Electrochemical Society, 152 共11兲 C738-C743 共2005兲 C739

Figure 1. Current-voltage curves for gold in 250 mM Na2HPO4 共dotted

Figure 2. Current-time transients for deposition of platinum at potentials
line兲, and in 250 mM Na2HPO4 and 17 mM 共NH4兲2PtCl6 共solid line兲 solu-
between −0.3 and −0.8 V. The inset shows the current density 共at t
tion. In the presence of PtCl2−
6 , reproducible scans were obtained after about = 2000 s兲 plotted vs deposition potential.
five cycles. The scan rate was 50 mV s−1.

current is almost independent of time, consistent with attachment-

were then introduced into the UHV chamber 共 Pbase ⬍ 2
controlled growth. At more negative deposition potentials, the depo-
⫻ 10−8 Torr兲 equipped with a fast entry load-lock cell. All spectra sition current decreases with time although much slower than the
were referenced to the C 1s peak at 284.6 eV. t−1/2 dependence for diffusion-limited growth. These results confirm
Results and Discussion that deposition is under mixed kinetic-diffusion control. The depo-
sition current densities obtained from the deposition transients are
Figure 1 shows current-voltage curves in supporting electrolyte shown in the inset in Fig. 2.
and in ammonium hexachloroplatinate solution. In the absence of These results illustrate that platinum can be deposited in a poten-
platinum ions, the current between +0.6 and −0.7 V is very small, tial range positive to the onset of hydrogen evolution, thereby avoid-
generally less than a few microamps. The onset of hydrogen evolu- ing effects associated with the codeposition of hydrogen. This is not
tion at about −0.75 V occurs close to the equilibrium potential at possible in acidic solutions where the equilibrium potential for hy-
this pH where Ueq共H+ /H2兲 = −0.71 V. drogen evolution is shifted positive by about 450 mV, close to the
The relevant equilibria involving platinum9 are onset of platinum deposition. Figure 3 shows the potential depen-
dence of the deposition efficiency, calculated assuming an overall
6 + 4e ↔ Pt + 6Cl
PtCl2− − −
Uⴰeq = 0.544 V 共Ag/AgCl兲 关1兴
four-electron reduction. Because the equilibrium potential for hydro-
gen is −0.71 V at this pH, proton reduction can be neglected at more
6 + 2e ↔ PtCl4 + 2Cl
PtCl2− − 2− −
Uⴰeq = 0.526 V 共Ag/AgCl兲
positive potentials. Thus at deposition potentials in the range
关2兴 −0.3 to − 0.7 V, the current is dominated by the reduction of plati-
num ions. At −0.3 V, close to the onset of bulk platinum deposition,
4 + 2e ↔ Pt + 4Cl
PtCl2− − −
Uⴰeq = 0.558 V 共Ag/AgCl兲 关3兴 the deposition efficiency is 0.43, implying that the reduction of
In the presence of Pt共IV兲Cl2− Pt共II兲 to Pt共0兲 is slower than for the reduction of Pt共IV兲 to Pt共II兲 at
6 , the onset of a reduction current
occurs at about 0.2 V. Since no Pt deposition is detected until about this potential. At −0.4 V, the deposition efficiency increased to
−0.3 V, the current in this region can be ascribed to the reduction of about 0.77, indicating that the reduction of Pt共II兲 to Pt共0兲 becomes
Pt共IV兲 to Pt共II兲 according to Reaction 2. The onset of platinum much faster in comparison to the reduction of Pt共IV兲 to Pt共II兲. The
deposition at −0.3 V coincides with a sharp increase in current and deposition efficiency decreases slightly between −0.4 and −0.7 V.
is followed by a peak at −0.5 V characteristic of nucleation and At −0.8 V, the deposition efficiency decreases to about 0.39 due to
diffusion-controlled growth. The overpotential for bulk platinum the contribution of hydrogen evolution to the total current, as can be
seen from the current—voltage curves shown in Fig. 1.
deposition is about 0.8 V, illustrating that the kinetics are very slow.
The scan rate dependence of the current peak is between ␻0.5 and
␻1.0, indicating that the attachment rate and ion transport rates are of
similar magnitude. At potentials negative to −0.7 V, the current in-
creases sharply due to hydrogen evolution. Since the exchange cur-
rent density for hydrogen evolution on platinum 共log兩i0兩 = 3.6兲 is
about two orders of magnitude larger than on gold 共log兩i0兩 = 5.5兲,10
the current is much larger in the presence of the deposited platinum
in comparison to the gold substrate.
On the positive scan, a small peak is seen at −0.7 V, due to
desorption of hydrogen from platinum deposited during the negative
scan. At potentials between −0.6 and −0.4 V, a diffusion-limited
deposition current of about 1 mA cm−2 is observed. Diffusion-
limited deposition extends to −0.3 V corresponding to the onset of
deposition in the forward scan. As expected, no stripping current is
seen at more positive potentials. On the second and subsequent
cycles, the current-voltage curves were highly reproducible.
Figure 2 shows a series of current-time transients for deposition
of Pt at potentials between −0.3 and −0.8 V. All the transients ex- Figure 3. Deposition efficiency vs deposition potential. The efficiency was
hibit an initial increase in current corresponding to the nucleation of determined from the deposition charge and the weight change assuming an
platinum islands. At a deposition potential of −0.3 V, the deposition overall four-electron reduction.
C740 Journal of The Electrochemical Society, 152 共11兲 C738-C743 共2005兲

Figure 4. Plan view scanning electron microscope images of platinum films deposited at a constant potential.

Figure 4 shows plan view scanning electron microscope images at 72.5, 74.9, and 77.9 eV. For Pt共II兲 in PtO, the Pt 4f doublet is
of platinum films deposited at constant potential. At a deposition shifted by about 1.1 eV, with peaks at 72.3 and 75.5 eV.11-14 Thus
potential of −0.3 V, close to the onset of deposition, the film is the three peaks seen for these films can be ascribed to Pt共II兲 and
smooth, bright, and has a very small grain size. At −0.4 V, the film Pt共IV兲 oxides. A very small contribution from Pt共0兲 at 71.5 eV in-
is also smooth and bright although the grain size is slightly larger. At dicates that the oxide layer at the surface is relatively thick because
−0.5 V, close to the deposition peak, the film is not as bright and the penetration depth at a take-off angle of 45° is about 3-4 ML.
clearly has a nodular structure with elongated, platelike grains. At The O 1s spectra for all of the films show a single peak at
−0.6 V, the film is matte gray with characteristic needlelike grains.
At −0.7 and −0.8 V, the films are characterized by angular grains
with relatively large elongated crystals. These results were very re-
producible and illustrate the strong dependence of film morphology
on deposition potential.
Figure 5a shows X-ray diffraction patterns for the platinum films
shown in Fig. 4. All films show strong 共111兲 peaks along with 共200兲,
共220兲, and 共311兲 peaks. With increasing deposition overpotential, the
films exhibit a much stronger 共111兲 texture, as can be seen from the
relative increase in the intensity of the 共222兲 peak compared to the
共200兲, 共220兲, and 共311兲 peaks. This can be seen more clearly in Fig.
5b, which shows the intensity ratio of the 共222兲 peak compared to
the 共200兲 and 共311兲 peaks. The 共222兲/共200兲 and 共222兲/共311兲 inten-
sity ratios are greater than 2 for deposition potentials of −0.7 and
−0.8 V, much larger than the ratios for untextured polycrystalline
films 关0.23 for 共222兲/共200兲 and 0.36 for 共222兲/共311兲兴, illustrating
the strong 共111兲 texture for the films deposited at these potentials.
The inset of Fig. 5b shows the 共311兲/共200兲 intensity ratio which is
close to 10 for films deposited at −0.3 and −0.4 V, much larger than
the value of 0.62 for a polycrystalline film, indicating that the films
deposited at these potentials have a strong 共311兲 texture.
From the 共200兲 and 共222兲 peaks in Fig. 5a, it can be seen that the
peak width decreases with increasing overpotential indicating that
the grain size increases with increasing overpotential. Figure 6
shows the grain size, determined from the X-ray peak broadening vs
the deposition potential. This figure shows that the lower limit of the
grain size increases from less than 5 nm at potentials close to the
onset of bulk platinum deposition to more than 20 nm at more nega-
tive potentials.
The surface composition of films was determined using X-ray
photoelectron spectroscopy. Figure 7 shows the Pt 4f and O 1s spec-
tra for the as-deposited platinum films. The Pt spectra for the films
deposited at −0.5, −0.6, −0.7, and −0.8 V all exhibit a well defined
doublet corresponding to the Pt 4f7/2 and Pt 4f5/2 peaks. The binding
energies of 71.5 and 74.8 eV are very close to the values of 71.2 and
Figure 5. 共a兲 X-ray diffraction patterns for platinum films as a function
74.5 eV reported for metallic Pt共0兲.11-14 For Pt共IV兲 in PtO2, the Pt 4f
of deposition potential. 共b兲 Intensity ratios for 共222兲/共200兲 and 共222兲/共311兲
doublet is shifted to higher binding energies by about 2.9 to 74.1 eV obtained from X-ray diffraction patterns vs deposition potential. The
and 77.4 eV.11-14 Thus the very small peak at about 77.9 eV can be solid symbols indicate the intensity ratios for untextured polycrystalline
assigned to Pt共IV兲 in a thin, compact PtO2 layer at the surface; the films: 共222兲/共200兲 = 0.23 and 共222兲/共311兲 = 0.36. The inset shows the
associated Pt 4f7/2 peak is superimposed on the Pt 4f5/2 for Pt共0兲 at 共311兲/共200兲 intensity ratio. For an untextured polycrystalline film,
74.8 eV. The films deposited at −0.3 and −0.4 V exhibit three peaks 共311兲/共200兲 = 0.62.
 Journal of The Electrochemical Society, 152 共11兲 C738-C743 共2005兲 C741

Figure 6. Apparent grain size, determined from the X-ray peak broadening,
vs the deposition potential.

531 eV. The oxygen 1s peaks in bulk PtO and PtO2 are at 530.3 and
530.5 eV, respectively.11-14 Due to the very low signal for the films
deposited at −0.5, −0.6, −0.7, and −0.8 V, it is not possible to
resolve the differences in the oxygen spectra. Thus the spectra indi-
cate the presence of a thin PtO2 oxide layer on films deposited at
−0.5, −0.6, −0.7, and −0.8 V, and a much thicker oxide of PtO2 and
PtO on films deposited at −0.3 and −0.4 V.
XPS spectra obtained after argon ion etching of films deposited
at all potentials reveal only Pt共0兲 peaks and no oxygen peaks, illus-
trating that the mixed oxide formed at low overpotentials is a sur-
face effect. At low overpotentials, close to the onset potential for
deposition at −0.3 V, the surface concentration of Pt共II兲 is expected
to be high and hence the formation of a mixed oxide may be related
to oxidation of adsorbed Pt共II兲 intermediates after deposition is com-
pleted. The formation of a mixed oxide is also correlated with strong
共311兲 texture and very small apparent grain size.
The electrochemical properties of the platinum films were depen-
dent on the deposition potential. Figure 8 shows cyclic voltammo-
grams for the electrodeposited platinum films and an annealed plati-
num foil in 50 mM H2SO4. The voltammogram for the platinum foil
exhibits the characteristic features of a polycrystalline film 共e.g.,
Ref. 15兲. Two hydrogen adsorption and two desorption peaks are
clearly distinguished. At positive potentials, the onset of oxygen
adsorption is followed by a current plateau up to the onset of oxygen
evolution. This plateau is comprised of a series of peaks associated
with platinum oxidation 关PtOx, Pt共OH兲y, etc.兴.16-18 On the reverse
scan, a relatively sharp oxide reduction peak is seen at 0.47 V.
Thin films deposited at −0.3 and −0.4 V exhibit poorly defined Figure 7. Pt 4f and O 1s XPS spectra for electrodeposited platinum films.
hydrogen adsorption and desorption peaks. This effect can be as- The deposition potentials are indicated on the figures.
cribed to the differences in the oxide layer and crystal orientation.
The loss of hydrogen peak definition and a negative shift in the
potential of the oxide reduction peak are often associated with the
formation of ␤-platinum oxide19,20 that is not completely reduced at and desorption peaks, relatively broad double layer regions, an oxi-
negative potentials.21 As shown above, the films deposited at −0.3 dation plateau, and a well defined oxide reduction peak. The films
and −0.4 V do not exhibit the compact PtO2 oxide usually associ- deposited at these potentials also exhibit strong 共111兲 texture and
ated with the air formed film on platinum. Hydrogen adsorption is relatively large grain size compared to the films deposited at more
also dependent on crystal orientation22,23 and hence the very small negative potentials.
grain size and preferred 共311兲 texture of the films deposited at these Figure 9 shows the surface roughness, determined from the hy-
potentials may also contribute to the differences in the hydrogen drogen desorption charge, plotted vs the film deposition potential.
adsorption and desorption peaks. The surface roughness factors for the films deposited at −0.5 and
The current densities associated with the films deposited at −0.5 −0.6 V are 79 and 52, respectively, consistent with the very rough
and −0.6 V are larger than for the other films, as expected from the morphologies seen in Fig. 4. At all other deposition potentials, the
very rough surface morphology, as shown in Fig. 4. The voltammo- surface roughness factors are less than 5.
gram for the film deposited at −0.5 V is sheared, indicating a rela- Because the hydrogen adsorption and desorption peaks are de-
tively high resistance, and exhibits poorly defined hydrogen pendent on crystal orientation,22,23 the films were further character-
adsorption/desorption peaks. These effects are related to the high ized by recording voltammograms in solution containing 50 mM
surface area and the small crystallite size. The voltammograms for H2SO4 and 1 mM CuSO4. Figure 10 shows cyclic voltammograms
the films deposited at −0.6, −0.7, and −0.8 V are similar to that of for an annealed platinum foil in 50 mM H2SO4 with and without
the annealed platinum foil with well defined hydrogen adsorption 1 mM CuSO4. Between the oxide reduction peak at 0.42 V and the
C742 Journal of The Electrochemical Society, 152 共11兲 C738-C743 共2005兲
Figure 8. Current-voltage curves for an annealed polycrystalline platinum
foil and electrodeposited platinum films in 50 mM H2SO4. The deposition
potentials are indicated in the figure. The scan rate was 10 mV s−1.
onset of bulk copper deposition at 0.10 V, several overlapping un-
derpotential deposition peaks are observed. On the reverse scan,
four stripping peaks can be resolved in the potential range from
Figure 9. Surface roughness factor vs deposition potential. 共䊊兲 Surface
roughness determined from the hydrogen desorption charge 共assuming
220 ␮C cm−2 for monolayer desorption兲, and 共䉭兲 surface roughness deter-
mined from the copper UPD stripping charge 共after subtracting the back-
ground charge兲.
Figure 10. Current-voltage curves for an annealed, polycrystalline platinum
foil in 50 mM H2SO4 共dotted line兲 and 50 mM H2SO4 and 1 mM CuSO4
共solid line兲 over the potential range −0.20 to 1.25 V at a scan rate of
10 mV s−1.
0.1 to 0.5 V. The stripping charge, after subtracting the current for
the films in the absence of CuSO4, was 481 ␮C cm−2, close to the
value of 440 ␮C cm−2 reported for a monolayer of copper on poly-
crystalline platinum.24 These results are consistent with the features
of Cu UPD on polycrystalline platinum reported in the literature
共Ref. 22 and references cited therein兲.
Figure 11 shows voltammograms in the potential range from
0.1 to 0.7 V after holding the potential at 0.1 V for 10 s to allow for
complete monolayer deposition. The films deposited at −0.4 and
−0.7 V exhibit UPD peaks similar to those observed for the an-
nealed foil, although the relative intensity of the individual peaks
varied somewhat. The voltammograms for the high surface area
films deposited at −0.5 and −0.6 V exhibit significant attenuation of
the peaks at more negative potentials. For these high surface area
films, the formation of a complete monolayer requires diffusion of
copper ions from the bulk solution to the interior of the film and the
10 s hold time at 0.1 V is insufficient to allow completion of the
Figure 11. Current-voltage curves for an annealed, polycrystalline platinum
foil and electrodposited platinum films in 50 mM H2SO4 共dotted line兲 and
50 mM H2SO4 and 1 mM CuSO4 共solid line兲 in the UPD region from
0.1 to 0.7 V. The scan rate was 10 mV s−1. In all cases the potential was
held at 0.10 V for 10 s before initiating the scan at 0.1 V.
 Journal of The Electrochemical Society, 152 共11兲 C738-C743 共2005兲
Figure 12. Current-voltage curves for platinum films deposited at 共a兲 −0.5 V
and 共b兲 −0.6 V in 50 mM H2SO4 共dotted line兲 and 50 mM H2SO4 and 1 mM
CuSO4 共solid line兲 in the UPD region from 0.1 to 0.7 V. The scan rate was
10 mV s−1. The potential was held at 0.10 V for 10, 100, 1000, 10,000, and
50,000 s prior to recording each curve. 共c兲 Plot of UPD stripping charge vs
the hold time at 0.1 V.
UPD process. Figure 12 shows voltammograms for the films depos-
ited at −0.5 and −0.6 V with hold times at 0.1 V up to 50,000 s. The
UPD stripping charge, after background subtraction, increases with
increasing hold time and eventually reaches a constant value, as
shown in Fig. 12c. With increasing hold times, the characteristic
UPD stripping peaks observed for the annealed foil begin to emerge.
A composite plot of the stripping scans after complete monolayer
formation is shown in Fig. 13. The stripping currents seen for the
films deposited at −0.5 and −0.6 V are considerably larger due to
the rough morphologies. The roughness factors determined from the
stripping charge are plotted in Fig. 9. This figure shows good agree-
ment between the roughness factors obtained from the hydrogen
desorption and the copper UPD stripping peaks.
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C743
Figure 13. Current-voltage curves for an annealed platinum foil and elec-
trodeposited platinum films. The annealed foil and films deposited at −0.4
and −0.7 V were held at 0.1 V for 10 s prior to the scan. The films deposited
at −0.5 and −0.6 V were held at 0.1 V for 10,000 s prior to the scan. The
scan rate was 10 mV s−1.
Conclusion
The morphology, microstructure, and electrochemical properties
of platinum thin films deposited from aqueous ammonium hexachlo-
roplatinate are highly dependent on the deposition potential. With
increasing overpotential, the grain size increases and the films ex-
hibit stronger 共111兲 texture. Films deposited at −0.5, −0.6, −0.7, and
−0.8 V exhibit a thin PtO2 surface oxide, whereas films deposited at
−0.3 and −0.4 V exhibit a thicker oxide consisting of PtO and PtO2.
Films deposited at low overpotential exhibit very small grain size
and a preferred 共311兲 texture. In addition, films deposited at −0.5
and −0.6 V are porous with very high surface areas.
Johns Hopkins University assisted in meeting the publication costs of
this article.
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