Electrochemistry Communications 11 (2009) 2184–2186

Contents lists available at ScienceDirect

Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Electrochemical deposition of ZnO in a room temperature ionic liquid:

1-Butyl-1-methylpyrrolidinium bis(trifluoromethane sulfonyl)imide
E. Azaceta a, R. Tena-Zaera a,*, R. Marcilla a, S. Fantini b, J. Echeberria c, J.A. Pomposo a,
H. Grande a, D. Mecerreyes a
a
New Materials Department, CIDETEC, Centre for Electrochemical Technologies, Parque Tecnológico de San Sebastián, Paseo Miramón 196, Donostia-San Sebastián 20009, Spain
b
Solvionic, Chemin de la Loge, Toulosse 31078, France
c
CEIT, San Sebastian 20018, Spain

a r t i c l e i n f o a b s t r a c t

Article history: An innovative electrochemical route is proposed to deposit nanocrystalline ZnO films. The approach is
Received 3 August 2009 based on the electrochemical reduction of O2 in a solution of zinc bis(trifluoromethanesulfonyl)imide salt
Received in revised form 5 September 2009 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide room temperature ionic liquid.
Accepted 23 September 2009
The mechanisms involved in the deposition process are analyzed by cyclic voltammetry, pointing out that
Available online 26 September 2009
the ZnO formation occurs from the chemical reaction between the Zn2+ and O 2 generated from the O2
reduction. Homogenous films constituted of primary ZnO nanocrystals (15–25 nm) assembled in close-
Keywords:
packed desert rose-like and open-packed round-top shape agglomerates are obtained at 100 and
ZnO
Electrodeposition
150 °C, respectively. The differences with respect to the electrochemical routes based on aqueous and
Ionic liquid organic media are discussed.
Nanocrystalline film Ó 2009 Elsevier B.V. All rights reserved.
1-Butyl-1-methylpyrrolidinium
bis(trifluoromethanesulfonyl)imide
Metal oxide

1. Introduction
The research attention on ZnO has enormously increased during
the past years due to its multi-functionality [1] resulting from the
unique combination of physical properties [2] and extremely rich
family of nanostructures [3]. Since the pioneering studies by Lin-
cot’s and Izaki’s groups [4,5], electrodeposition has emerged as a
promising technique to deposit ZnO at low temperature. Although
there are a few studies dealing with organic solvents such as pro-
pylene carbonate [6] or dimethylsulfoxide [7], most of the electro-
chemical approaches are based on aqueous electrolytes [5,8]. The
dimensions [8,9], crystal orientation [10] and electrical properties
[11] of ZnO nanostructures have been successfully modified by
playing with the nature and concentration of the additional anions
in the electrolyte. In this framework, ionic liquids (ILs) appear to be
a highly attractive media to be used as a versatile source of anions
for the ZnO electrodeposition.
The electro(chemical) and physical properties of ILs have been
exploited to electrodeposit several metals and semiconductors
[12–14]. However, to our best knowledge, there are no reports
on the electrodeposition of metal oxides in ILs. Because the forma-
tion of hydroxide ions does not take place from the oxygen reduc-
tion in aprotic ILs [15,16], electrolytes based on the latter may be
crucial to avoid spurious hydroxide phases (e.g. Znx(OH)yClz [5]
and Zn(OH)2 surface traces [17]). Furthermore, the negligible vapor
pressure of ILs allows the deposition at temperatures higher than
100 °C. This may also be a key to improve the ZnO quality by
decreasing the content of intrinsic defects such as zinc interstitials,
which are highly sensitive to temperature. From the practical point
of view air-stable room temperature ILs are especially attractive.
As an example, 1-butyl-1-methylpyrrolidinium bis(trifluorome-
thane sulfonyl)imide (PYR14TFSI) has recently attracted large inter-
est as an electrolyte for electrodeposition [12,14,18].
In this communication, we report on an innovative route to ob-
tain ZnO nanocrystalline layers from the electrochemical reduction
of O2 in PYR14TFSI containing Zn2+ cations. The electro(chemical)
mechanisms involved in the deposition are discussed. The mor-
phology and structural properties of the obtained films are also
analyzed, emphasizing the differences with respect to those ob-
tained by the electrochemical approaches based on aqueous and
conventional organic electrolytes.
2. Experimental section

* Corresponding author. Tel.: +34 943 309 022; fax: +34 943 309 136. Fluorine doped tin oxide coated (TEC15, Hartford Glass) glasses
E-mail address: rtena@cidetec.es (R. Tena-Zaera). were used as a substrate. The experiments were performed in a

1388-2481/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2009.09.026
 E. Azaceta et al. / Electrochemistry Communications 11 (2009) 2184–2186
three-electrode electrochemical cell with the substrate as the
working electrode, a Pt sheet as the counter electrode and a Pt wire
as the pseudo-reference electrode. The electrolyte was not stirred
and consisted of a 5  103 M solution of zinc bis(trifluorometh-
anesulfonyl)imide (Zn(TFSI)2) in PYR14TFSI (purity 99.9%, H2O <
0.005%) IL, saturated with O2 (Praxair, 99.999%, H2O < 2 ppmv).
The Zn(TFSI)2 was chosen to avoid some possible anion exchanges
with the PYR14TFSI and the consequent formation of spurious spe-
cies. Both chemicals were provided by Solvionic and no further
purification process was performed.
The electrochemical cell was placed in a hot silicon oil bath
which temperature was controlled in 100–150 °C range. Electrode-
positions and cyclic voltammetry (CV) measurements were carried
out using an Autolab PGSTAT302N and GPES software (Eco Chemie
B.V.). CV experiments were performed at 100 °C for pure IL (purged
by Ar flow), each independent precursor (O2 and Zn(TFSI)2) solu-
tion and for the full deposition electrolyte. Scans were performed
at a rate of 50 mV/s. Because the stability of the pseudo-reference
electrode was checked by using a solution of ferrocene in PYR14TF-
SI, all potentials hereafter will be referred to Fc/Fc+. The electrode-
positions were carried out at 100 and 150 °C under 1.6 V and the
charge density was 0.5 C/cm2.
The morphology and crystalline structure of the films were ana-
lyzed using a JEOL-JSM-7000F field emission scanning electron
microscope (FESEM) and a Bruker AXS-D8 Advance X-ray diffrac-
tometer (XRD) using Cu Ka radiation.
3. Results and discussion
At first, the electrochemical behavior of the precursor (O2 and
Zn(TFSI)2) solutions and full electrolyte were analyzed by CV. The
voltammograms are showed in Fig. 1. The data from Ar bubbled
PYR14TFSI is also included to show that, in good agreement
with reference [18], the IL does not exhibit significant current
contribution.
For the oxygen bubbled PYR14TFSI, the onset of a cathodic cur-
rent occurs at approximately 0.9 V resulting in a wave (centered
around 1.2 V, inset b of Fig. 1) followed by a considerable increase
of the current for potentials more negative than 1.7 V. With re-
spect to the anodic current, a wave centered around –1.0 V is ob-
served (Fig. 1, inset a). According to the previous studies [15,16],
both waves can be attributed to the O2/O 2 redox couple (Eq. 1)
and the increase of the cathodic current (for V < 1.7 V) may be
Fig. 1. Voltammograms of different solutions: (line) Ar purged PYR14TFSI, (j) O2
bubbled PYR14TFSI, (s) Zn(TFSI)2 dissolved in PYR14TFSI and (N) full electrolyte
(PYR14TFSI + Zn(TFSI)2 + O2). The insets a and b show magnified views of some
anodic and cathodic features.
2185
2
due to reduction of the superoxide (O 2 ) to peroxide (O2 ) ions.
For the Zn(TFSI)2 solution, the onset of the cathodic current ap-
pears near –1.1 V and a pair of cathodic/anodic waves is clearly ob-
served and attributed to reduction and oxidation of the Zn2+/Zn
redox couple, respectively, (Eq. 2). By comparing the voltammo-
grams from both precursor (O2 and Zn2+) solutions, a potential
window larger than 0.2 V would be in principle available to obtain
zinc oxide phases (ZnxOy, where x and y will be determined by the
stability of ZnO4 and ZnO2 in the media [19]) by Eq. 3.
O2 þ e $ O2 ð1Þ
Zn2þ þ 2e $ Zn ð2Þ
Zn2þ þ 2O2 $ ZnO4 $ ZnO2 þ O2 $ ZnO þ 3=2O2 ð3Þ
Surprisingly, the voltammogram of the full electrolyte exhibits
the onset of the cathodic current at 1.2 V, which is considerably
more negative than that detected for the O2 reduction in the pure
PYR14TFSI. This could be due the adsorption of some species (most
probably Zn2+) on the substrate surface, affecting the O2 reduction.
Although the voltammogram of the full electrolyte exhibits catho-
dic features very similar to those from the Zn(TFSI)2 solution, no
anodic current is detected in the former. The absence of the Zn/
Zn2+ signature allows to rule out the reduction of Zn2+ during the
cathodic sweep. The oxygen reduction is thus proposed to be the
main contribution to the cathodic current. Zn2+ cations provided
by the Zn(TFSI)2 salt are then available to react with the superoxide
ions, giving ZnxOy compounds (Eq. 3). The reduction of superoxide
to peroxide ions is therefore quenched (no increase of cathodic
current for potentials <1.7 V). Additional, the consumption of
the O 2 (Eq. 3) may displace the equilibrium of the oxygen reduc-
tion reaction (Eq. 1) towards the right side. Although this can con-
tribute to the relative increase of the cathodic current (with respect
to the O2 bubbled PYR14TFSI for potentials from 1.2 to 2.0 V)
other phenomena such as the catalytic properties of the Zn2+
may also be involved [20]. CV points out therefore that the electro-
deposition of ZnxOy compounds in PYR14TFSI ionic liquid is possible
and takes place in a different way than in aqueous media because
hydroxide ions are not involved.
To gain a further insight, electrodepositions under potentiostat-
ic conditions (V = 1.6 V) were performed at 100 °C. As a result,
transparent and uniform at naked eye films were obtained.
Fig. 2a–c displays the SEM micrographs of the samples. Although
the films exhibit some micro-cracks, they consist generally of
close-packed desert rose-like agglomerates constituted of ‘‘petals”
of hundreds of nanometers in length and less than 50 nm in thick-
ness. The ‘‘petals” posses some nanoscale features (Fig. 2b, inset),
suggesting that they are constituted of very small grains
(<20 nm) arranged perpendicularly to the substrate (Fig. 2c). Elec-
trodepositions at 150 °C were also performed. Crack-free films con-
stituted of open-packed agglomerates with round-top shape were
then obtained (Fig. 2d–f). The agglomerates are 200–300 nm in
diameter and are constituted of grains of 20–30 nm in size
(Fig. 2d, inset). The adsorption of the IL moieties onto the ZnO sur-
faces, hindering the grain growth may be the origin of the small
grains. The packing density and order of the grains seem to be
highly sensitive to the deposition temperature, opening wide pos-
sibilities to design the film morphology which is interesting for fu-
ture applications.
Fig. 3 displays the XRD patterns of the samples. Compared with
the pattern from the substrate, diffraction peaks characteristics of
the ZnO wurtzite phase [21] are clearly detected indicating that
ZnO was electrodeposited and excluding detectable traces of Zn.
The crystallite size was estimated from the width of the (1 0 1  1)
peak by using the Scherrer’s formula. Values of 17 and 23 nm were
2186 E. Azaceta et al. / Electrochemistry Communications 11 (2009) 2184–2186
Fig. 2. SEM micrographs of the top view and cross section of films obtained at 100
(a–c) and 150 °C (d–f). The insets show magnified views (bar scales: 100 nm) of the
agglomerates.
Fig. 3. XRD patterns of the substrate and samples electrodeposited at 100 and
150 °C. The inset shows a magnified view of the patterns for the 2h range of 30–38°.
obtained for the films deposited at 100 and 150 °C, respectively.
Although the values can be slightly underestimated due to instru-
mental or strain contributions to the peak broadening, they are in
agreement with the primary grain size inferred from SEM micro-
graphs. Small ZnO crystals are therefore assembled to form
agglomerates of hundred nanometers in size. By comparing the rel-
 0), (0 0 0 2) and (1 0 1
ative intensity of (1 0 1  1) peaks with respect
to those from a randomly oriented powder sample [21], a slight
 0] direction is found for
preferential orientation along the [1 0 1
the films deposited at 100 °C. This fact emphasizes some order in
the arrangement of the primary crystals. In contrast, no preferen-
tial orientation is detected for that obtained at 150 °C. The temper-
ature seems thus to affect not only the grain growth, but also their
assembly. This could be due to the temperature effect in the inter-
action between the IL moieties and ZnO surfaces. The adsorption of
TFSI anions in as deposited samples (rinsed generously with ace-
tone) is inferred by Fourier Transform Infrared spectroscopy (char-
acteristic signatures of TFSI) and Energy Dispersive X-ray (traces of
F and S), irrespectively of the deposition temperature. However,
the EDX traces and FTIR peaks disappear generally after immersing
the samples in acetone for long time. Further studies are necessary
to gain a better understanding of the interactions between IL moi-
eties and ZnO and the influence on its growth mechanism and
properties.
4. Conclusions
ZnO nanocrystalline layers have been electrodeposited in
PYR14TFSI ionic liquid at temperatures P100 °C, by taking advan-
tage of its negligible vapor pressure. Cyclic voltammetry has been
performed to study the involved mechanism, pointing out that the
ZnO formation occurs from the chemical reaction between the
Zn2+ and superoxide ions (O 2 ), that are generated from the O2
reduction. The ZnO is therefore formed in a different way than in
the aqueous media and zinc hydroxides are not involved. In con-
trast to the conventional aprotic organic solvents, the IL moieties
seem to affect the grain growth as well as their assembly in a sig-
nificant manner. This opens wide possibilities for the electrodepos-
ition of innovative ordered structures by nanocrystal assembly,
which have been scarcely obtained in other electrolytes.
Acknowledgments
Financial support by the Spanish Ministry of Science and
Innovation (HOPE CSD2007-0007 (Consolider-Ingenio 2010)) and
Basque Government (i-NANOGUNE Etortek) is gratefully acknow-
ledged. R.T.-Z. acknowledges the support of the Program ‘‘Ramón
y Cajal” of the MICINN.
References
[1] C. Klingshirn, Chem. Phys. Chem. 8 (2007) 782.
[2] U. Ozgur, Y. Alivov, C. Liu, A. Teke, M. Reshchikov, S. Dogan, V. Avrutin, S.J. Cho,
H. Morkoç, J. Appl. Phys. 98 (2005) 041301.
[3] Z.L. Wang, Mater. Today 7 (2004) 26.
[4] M. Izaki, T. Omi, Appl. Phys. Lett. 68 (1996) 2439.
[5] S. Peulon, D. Lincot, J. Electrochem. Soc. 145 (1998) 864.
[6] B. O’Regan, V. Sklover, M. Grätzel, J. Electrochem. Soc. 148 (2001) C498.
[7] D. Gal, G. Hodes, D. Lincot, H.W. Schock, Thin Solid Films 361–362 (2000) 79.
[8] R. Tena-Zaera, J. Elias, C. Lévy-Clément, I. Mora-Sero, Y. Luo, J. Bisquert, Phys.
Stat. Solidi A 205 (2008) 2345 (and references therein).
[9] J. Elias, R. Tena-Zaera, C. Lévy-Clément, J. Phys. Chem. C 112 (2008) 5736.
[10] T. Yoshida, M. Tochimoto, D. Schlettwein, D. Wohrle, T. Sugiura, H. Minoura,
Chem. Mater. 11 (1999) 2657.
[11] R. Tena-Zaera, J. Elias, C. Lévy-Clément, C. Bekeny, T. Voss, I. Mora-Seró, J.
Bisquert, J. Phys. Chem. C 112 (2008) 16318.
[12] A.P. Abbott, K.J. McKenzie, Phys. Chem. Chem. Phys. 8 (2006) 4265.
[13] F. Endres, M. Bukowski, R. Hempelmann, H. Natter, Angew. Chem. Int. Ed. 42
(2003) 3428.
[14] F. Endres, A.P. Abbot, D.R. MacFarlane, Electrodeposition from Ionic Liquids,
Wiley–VCH Verlag GmbH and Co. KGaA, Weinheim, 2008.
[15] Y. Katayama, H. Onodera, M. Yamagata, T. Miura, J. Electrochem. Soc. 151
(2004) A59.
[16] R.G. Evans, O.V. Klymenko, S.A. Saddoughi, C. Hardacre, R.G. Compton, J. Phys.
Chem. B 108 (2004) 7878.
[17] D. Pradhan, K.T. Leung, Langmuir 24 (2008) 9707.
[18] S. Randström, G.B. Appetecchi, C. Lagergren, A. Moreno, S. Passerini,
Electrochim. Acta 53 (2007) 1837.
[19] H.A. Wriedt, Bull. Alloy Phase Diag. 8 (1987) 166.
[20] T. Yoshida, D. Komatsu, N. Shimokawa, H. Minoura, Thin Solid Films 451–452
(2004) 166.
[21] Powder Diffraction File 00-036-1441, PDF-2 Database Sets, International
Center for Diffraction Data, Newton Square, PA 1993.