Electrochimica Acta 178 (2015) 45–54

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrosynthesis and characterization of ZnO nanoparticles as

inorganic component in organic thin-film transistor active layers
Rosaria Anna Picca a,∗,1 , Maria Chiara Sportelli a , Diana Hötger b , Kyriaki Manoli a ,
Christine Kranz b , Boris Mizaikoff b , Luisa Torsi a , Nicola Cioffi a,∗
a
Dipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, via E. Orabona 4 70126 Bari, Italy
b
Universität Ulm Institut für Analytische und Bioanalytische Chemie, Albert Einstein Allee, 11–89081, Ulm, Germany

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

Article history: ZnO nanoparticles have been prepared via a green electrochemical synthesis method in the presence
Received 8 June 2015 of a polymeric anionic stabilizer (poly-sodium-4-styrenesulfonate, PSS), and then applied as inorganic
Received in revised form 16 July 2015 component in poly-3-hexyl-thiophene thin-film transistor active layers. Different parameters (i.e. current
Accepted 20 July 2015
density, electrolytic media, PSS concentration, and temperature) influencing nanoparticle synthesis have
Available online 26 July 2015
been studied. The resulting nanomaterials have been investigated by transmission electron microscopy
(TEM) and spectroscopic techniques (UV-Vis, infrared, and x-ray photoelectron spectroscopies), assessing
Keywords:
the most suitable conditions for the synthesis and thermal annealing of nanostructured ZnO. The proposed
Nanostructured oxide
Electrochemical-thermal synthesis
ZnO nanoparticles have been successfully coupled with a poly-3-hexyl-thiophene thin-film resulting in
Poly(sodium 4-styrenesulfonate) thin-film transistors with improved performance.
Metal oxide semiconductor © 2015 Elsevier Ltd. All rights reserved.
OFET.

1. Introduction [21,22]. This is a peculiar feature of nanostructured ZnO since other

The application of metal oxides in the form of nanoparticles
(NPs) and thin films is continuously expanding, ranging from their
use in photo-catalysis to opto-electronics and in solar cells, but
metal oxides are also used in electrical, biomedical and sensor
applications [1–5]. Among metal oxide NPs, ZnO nanomaterials
have attracted the interest of scientists and technologists because
of their excellent electrical and physicochemical properties in the
last decades. Zinc oxide is a versatile wide band-gap semiconductor
(3.1-3.4 eV) and has a large excitation binding energy of 60 meV at
room temperature [6]. It has also tunable opto-electronic proper-
ties and piezoelectric features [7]. Zinc oxide is also an attractive
material for the development of thin-film transistors (TFT) [8–15].
Interestingly, this nanostructured oxide has been proposed not
only to build up n-type TFTs [16], but also hybrid organic-inorganic
materials -either as composites or bilayers- for high-performance
and stable devices, such as hybrid solar cells [17,18], light-emitting
organic field effect transistors (LE-OFETs) [19,20], OFET gas sensors
∗ Corresponding author. Tel.: +390805442020; fax: +390805442026.
E-mail addresses: rosaria.picca@uniba.it (R.A. Picca), maria.sportelli@uniba.it
(M.C. Sportelli), D.Hoetger@fkf.mpg.de (D. Hötger), kyriaki.manoli@uniba.it
(K. Manoli), Christine.kranz@uni-ulm.de (C. Kranz), boris.mizaikoff@uni-ulm.de
(B. Mizaikoff), luisa.torsi@uniba.it (L. Torsi), nicola.cioffi@uniba.it (N. Cioffi).
1
ISE Member; division: Electrochemical Materials Science.
semiconductor oxides (e.g., V2 O5 , MO3 , WO3 , TiO2 ) have been
mainly proposed as interlayers between the organic semiconductor
and metal contacts in organic TFTs (OTFTs) [23]. In general, metal
oxides such as titanium dioxide (TiO2 ) are used as high-k materials
in order to increase the capacitance of the dielectric layer and lower
the operating voltage of the device [24]. Moreover, in solar cell
processing, ZnO has also proven to be more stable than TiO2 under
air conditions [25]. Regarding TFT fabrication, either ZnO thin films
or ZnO nanoparticles (ZnO NPs) were used. The latter can be syn-
thesized by several methods [26,27] and among the alternatives,
electrochemical approaches are emerging as advanced solutions. In
general, they can be considered particularly appealing due to their
efficiency, versatility, and scalability. The use of aqueous media
has often been reported, which also makes them “environmentally
friendly” [28,29]. Moreover, a control over electrosynthesis param-
eters (electrolyte composition, applied potential, current density,
etc.) affords for additional strategies to tune the nanomaterials’
ultimate properties [30]. In this field, a pioneering paper on size-
selective synthesis of colloidal core-shell metal nanoclusters (Pd,
Ni, etc.) by a pure electrochemical method was proposed by the
group of Reetz more than twenty years ago [31], which produced
a cascade of subsequent studies [32–34]. Therein, an electrolyte
composed of acetonitrile and tetrahydrofuran (ACN/THF 4:1) in
the presence of tetraoctylammonium bromide (TOAB) as capping
agent was used applying a moderate current density of 0.1 mA/cm2 .

http://dx.doi.org/10.1016/j.electacta.2015.07.122
0013-4686/© 2015 Elsevier Ltd. All rights reserved.
46 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54
Such an approach has been then exploited by the same group
for the production of colloidal inorganic oxides (specifically CoO)
[35], by simply insufflating air into the electrochemical cell after
the electrosynthesis of metallic clusters. This method was fur-
ther developed by Natter and Hempelmann, who were the first
proposing the EDOC (Electrochemical Deposition under Oxidizing
Conditions) method to prepare highly crystalline nanostructured
ZnO by insufflating air during the whole electrosynthesis [36,37].
Mahamuni et al. [38] used a zinc sheet as working electrode to pro-
duce ZnO quantum dots by the sacrificial anode electrolysis. The
synthesis was carried out under oxygen atmosphere in galvano-
static mode. This resulted in the production of ZnO quantum
dots (QDs). Several examples of ZnO electrosynthesis have been
performed in organic media, such as 2-propanol [37], ACN/THF
mixtures [39], methanol or ethanol [40–44]. With the exception
of electrodeposition of ZnO nanostructures from aqueous Zn(II)
salt baths [45–47], little is published about the synthesis of ZnO
in aqueous media. In 1997, considering the spontaneous oxidation
of Zn sheets in water, Kitano and Shiojiri [48] prepared ZnO NPs, at
dc voltages V > 100 V. This is probably the first example of aqueous
preparation of ZnO particles. In 2011, the Veith group [49] pro-
posed a synthesis using diluted acetic acid as electrolyte at 40 V
applied potential, and carefully studied the influence of tempera-
ture, insufflated gas, and sintering on the morphology and chemical
speciation of the as-prepared ZnO NPs. Other authors have reported
on the use of alkaline (rather than slightly acidic) conditions to
synthesize ZnO NPs at high potentials (20 - 40 V) [50] followed by
an annealing step to improve particle crystallinity. Few years ago,
Venkatesha and co-workers [51–53] have presented a two-step
method using NaHCO3 aqueous solution as electrolyte to gener-
ate mixed zinc carbonate and hydroxide species at low potentials
with a subsequent thermal treatment for the precursor decompo-
sition to ZnO NPs [51,52]. Based on these electrochemical–thermal
methods, we have developed a modified approach based on the use
of anionic stabilizers to better control the particle size, morphol-
ogy, and surface chemistry of ZnO NPs, galvanostatically grown in
aqueous media. Poly(sodium 4-styrenesulfonate) (PSS), often used
as stabilizer in sensing applications [54], was selected as dispersing
agent due to its biocompatibility, non-toxicity, and suitability for
printable electronics. Moreover, the negative charges from sulfate
groups carried by PSS could also promote the interaction with both
ZnO NPs and biomolecules, for perspective biosensing applications
[54]. In this work, different synthetic parameters, such as cur-
rent density, electrolyte composition and temperature, stabilizer
concentration, and thermal treatment, were studied to investigate
their influence on the ZnO NPs morphology and chemical compo-
sition. Moreover, the electrical properties of OTFTs modified by
ZnO NPs were evaluated, triggered by the proven NPs’ capability
to improve sensing performances [55], thus posing a basis for the
further development of ZnO-containing OTFT biosensors [56].
2. Experimental
2.1. Materials
Zinc sheets (1 mm thick, 99.99 + %) were purchased from Good-
fellow Ltd and cut into 2 × 1 cm pieces. Sodium bicarbonate (purum
p.a., ≥ 99.0%), 2-propanol (Chromasolv® Plus, for HPLC, 99.9%),
hydrochloric acid (ACS reagent, 37%), poly(3-hexylthiophene-2,5-
diyl) (P3HT, regioregular, electronic grade, 99.995% trace metal
basis, Mw ∼ 15.000–45.000, Rieke® Metals Inc.), Chloroform
(puriss. > 99.8%, ACS reagent), poly(sodium 4-styrenesulfonate)
(PSS, average Mw ∼ 70,000, powder), and potassium bromide (FT-
IR grade, ≥99% trace metals basis) were purchased from Sigma
Aldrich. Aluminum oxide (purum p.a., 99.7%), for the mechanical
polishing of zinc sheets, was obtained from Fluka Chemicals. p-
doped Si/SiO2 (Si:B, oxide: 300 nm, <110>) wafers were purchased
from Si-Mat Silicon Material. Gold pellets for thermal evaporation
(99.99%) were purchased from Gambetti Kenologia. Milli-Q water
was used throughout the experiments.
2.2. Experimental set-up
A three-electrode cell was employed to prepare ZnO NPs. The
cell was composed of two twin zinc sheets and an Ag/AgCl (in
saturated KCl) reference electrode. Zinc electrodes were firstly
polished using sandpaper, and afterwards using Al2 O3 powder.
Then, they underwent 3 cycles of sonication alternating Milli-
Q water and 2-propanol. The electrodes were then activated in
1 M HCl for 30 s [51]. The synthesized nanoparticles mass was
estimated by difference of zinc sheets weights, before and after
the process. The electrosynthesis was carried out galvanostatically
(j = 10 mA/cm2 ) for 1 h, under vigorous stirring at room temper-
ature, with a CH-1140b potentiostat-galvanostat (CH Instruments,
USA). The electrolytic medium was composed of 1 g/L PSS, dissolved
in 30 mM NaHCO3 aerated aqueous solution. pH was monitored
at the beginning and at the end of the synthesis. Afterwards, the
colloidal dispersion was centrifuged at 5000 rpm for 45 minutes.
The resulting precipitate was dried overnight at 70 ◦ C. The obtained
powder was finally calcined at 300 ◦ C or 600 ◦ C in a muffle furnace
for 1 h.
2.3. Morphological and spectroscopic characterization
Both dried and calcined powders were suspended in ultrapure
water (1 g/L) by sonication for 30 minutes, before TEM and UV-Vis
characterization. Pristine samples were diluted 1:9 with Milli-Q
water.
TEM microscopy was performed with a FEI Tecnai 12 instrument
(high tension: 120 kV; filament: LaB6 ), by dropping the NP suspen-
sion on a Formvar® -coated Cu grid (300 mesh, Agar Scientific). The
microscope was calibrated by using the S106 Cross Grating (2160
lines/mm, 3.05 mm) supplied by Agar Scientific. Alignments and
astigmatism correction were carried out following factory settings
and fast Fourier transform processing, respectively.
UV-Vis spectroscopy was carried out with a Shimadzu UV-1601
double beam spectrometer, equipped with a silicon photodiode
detector, from 200 to 800 nm, with 1-cm Quartz Suprasil® cuvettes
(Hellma Analytics).
FTIR spectra were collected on a BioRad FTS6000 instrument
with a DTGS detector in transmittance mode (resolution 4 cm−1 ,
range 4000–400 cm−1 ), and processed using the BIORAD WinIR Pro
software. Samples were prepared as KBr pellets, grinding a suffi-
cient quantity of ZnO nano-powder in an agate mortar.
Dried and calcined powders were characterized by means of
XPS, using a Thermo Fisher Scientific Theta Probe Spectrometer
equipped with a monochromatized AlK␣ source and beam spot
diameter of 300 ␮m. Samples were mounted onto the sample
holder by means of a double-side copper tape (Agar Scientific).
All XPS and Auger spectra were registered in constant analyzer
energy (CAE) mode. Survey and high-resolution spectra (C1s, O1s,
Zn2p, ZnL3 M45 M45 , S2p and Na1s) were acquired at pass ener-
gies of 150 and 100 eV, respectively, and with a step size of 1.0
and 0.1 eV, respectively. The influence of X-ray radiation on sam-
ple chemical environments was excluded by performing multiple
acquisitions of C1s and Zn2p spectra on sacrificial samples for a
duration longer than the optimized analysis time. Artifacts related
to massive sample damage upon irradiation and electron emission
were ruled out. Detailed spectra processing was performed by com-
mercial Thermo Avantage software (v. 4.75, © 1999–2010 Thermo
Fisher Scientific). Accurate curve-fitting analysis was applied to
 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54
the high-resolution spectra applying a Shirley background removal
and using an optimized database of Scofield sensitivity factors for
element quantification (expressed as At%) in a metal oxide environ-
ment. The same peak shape parameters (Gaussian/Lorentzian ratio
and full width at half maximum) values were utilized for the curve
fitting of components belonging to the same high-resolution spec-
trum. Spectra were corrected for charge compensation effects by
offsetting the binding energy relative to the aliphatic component
of the C1s spectrum, which was set at 284.8 eV. Modified Auger
parameter (␣ ) [57,58] was used to study the zinc chemical specia-
tion, since a poor spectroscopic resolution is expected for the Zn2p
main photoelectron emission [59,60].
2.4. OTFT preparation and characteristics measurements
OTFT devices were prepared on a highly p-doped silicon sub-
strate acting as the gate electrode (G). Thermally grown 300 nm
silicon dioxide (SiO2 ) was used as gate dielectric. The substrate sur-
face was cleaned by immersion in 2-propanol, for 15 minutes in an
ultrasonic bath, and then dried under nitrogen flow [61].
The procedure consisted in a two-step deposition using a
Laurell Technology Corporation spin coater (model WS–650
MZ–NPP/LITE). In the first step (A), 1 g/L of ZnO NP aqueous sus-
pension was spin-coated on a clean substrate, followed by the
deposition of a P3HT film onto it (2000 rpm, for 1 minute) from a
2.5 g/L P3HT chloroform solution. Different devices were prepared
with ZnO NPs calcined at 300 ◦ C or 600 ◦ C and selecting two rotation
speeds (300 or 2000 rpm) for step A.
Source (S) and drain (D) contacts were finally deposited by ther-
mal evaporation (8 × 10−7 torr) of gold through a shadow mask. The
resulting OTFTs had a bottom-gate/top-contact configuration. The
gate contact was obtained scratching SiO2 layer with a diamond
tip in order to reach the Si surface. The electrical performances of
the fabricated devices were then evaluated in air using a Keith-
ley 4200-SCS semiconductor parameter analyzer. OTFT channel
length (L) and width (W) were 200 ␮m and 4 mm, respectively.
Current–Voltage (I-V) output curves were registered by measur-
ing IDS (drain-source current) versus VDS (drain-source voltage)
at different gate bias VG values (ranging from 0 to -100 V in 10 V
steps). Transfer characteristics were measured by sweeping the
gate voltage (VG ) from +100 V to -100 V (4 V step) at constant drain
voltage (VDS = -100 V). In the latter case, the gate voltage was swept
from positive to negative values in order to identify any ambipolar
behavior. The values of mobility (␮), on-off current ratio (ION /IOFF ),
and threshold voltage (VT ) were extracted from transfer curves,
keeping VDS fixed at − 100 V and following the procedure reported
in [62].
3. Results and discussion
In a previous proceeding paper, we preliminarily demonstrated
the feasibility of the Chandrappa route to ZnO nanomaterials
synthesis [51], employing modified electrolyte baths and elec-
trosynthesis conditions [63]. In general, it is well accepted that
the use of different dispersing agents may allow a better morpho-
logical control of electro-produced nanostructures. In particular,
anionic species such as PSS are responsible for the anodic stabi-
lization of nanocolloids, improving also the reaction yield [63]. In
the present study, optimal conditions for the synthesis of ZnO NPs
were defined based on a detailed morphological and spectroscopic
characterization. It was found that PSS 1 g/L, room temperature and
a current density of 10 mA/cm2 are the best choice for carrying out
the electrochemical step. ZnO NPs were obtained by calcination
of electrosynthesized nanogels at temperatures above 300 ◦ C for
1 h. TEM images of pristine and calcined NPs are reported in Fig. 1.
47
Table 1
Variation of the electrosynthesis parameters, and yield of the process, obtained by
electrodes differential weighing.
Electrolytic media Current density Colloid Process yield
j [mA/cm2 ] concentration [g/L] (%)
NaHCO3 30 mM 10 1.63 47
PSS 1 g/L in 1 0.24 68
NaHCO3 30 mM
PSS 1 g/L in 5 1.43 82
NaHCO3 30 mM
PSS 1 g/L in 10 3.18 92
NaHCO3 30 mM
Good NP morphology was observed, especially for NPs calcined at
the highest temperature (Fig. 1b-c) showing a mean core diameter
of 46 ± 8 nm (Fig. 1d).
3.1. Influence of synthesis parameters on the production of ZnO
nanoparticles
3.1.1. Current density
Considering that the current density (j) applied during elec-
trosynthesis has effect on the size distribution of the obtained
particles [31,64], three different values were tested: 1, 5 and
10 mA/cm2 . As expected, the lower the current density, the lower
the amount of dissolved Zn. The use of dilute hydrogen carbon-
ate solutions for zinc corrosion was considered as it limits a fast
electrode passivation promoting the formation of dispersed white
flakes saturating the electrolytic medium [65–68]. In particular,
large nuclei of ZnO are hypothesized to grow as a thick oxide film
on the anode [65] and porous structures are formed under these
conditions allowing the process to last for several minutes [68].
Furthermore, we observed that the addition of a charged stabilizer
could extend the duration of the synthesis over this time.
The process yield was calculated as the ratio between the exper-
imental and the theoretical mass of nanodispersed zinc, showing a
remarkable increase with j. The experimental value was obtained
by weighting the zinc electrodes before and after electrosynthesis,
while the theoretical mass was calculated through the Faraday’s
law equation in terms of a 2-electron process. Average nanodis-
persed zinc mass (mZn ) and process efficiency are reported in
Table 1.
The as-prepared gels obtained at different current densities
were characterized by TEM (Fig. 2) showing an irregular and unde-
fined morphology in a sol-like state.
XPS and FTIR characterizations were performed to investigate
the chemical composition of the collected colloids. XPS analysis of
the samples prepared at different current densities showed that,
below 10 mA/cm2 , Zn(II) species are not predominant and Zn(0)
state is partially observed, probably due to a cathodic stabiliza-
tion [31]. This is demonstrated by the line shape and position
of ZnL3 M45 M45 (Fig. S1) signal falling at KE = 991.8 ± 0.1 eV. In
fact, this value and the corresponding modified Auger parameter
(␣’ = BEZn2p3/2 + KEZnL3M45M45 [69]) at 2012.1 ± 0.2 eV are interme-
diate between the values expected for Zn(0) and Zn(II) states
[59,60,70], thus suggesting their simultaneous presence. As a result,
a current density of 10 mA/cm2 was considered suitable for the
preparation of nanocolloids.
3.1.2. Electrolytic medium
Other media with similar pH (pH = 8) and ionic strength were
compared to NaHCO3 solution. NaCl 30 mM and borate buffer were
chosen using PSS 1 g/L as stabilizer. The increase in pH was con-
firmed in both cases, and a process yield of 89% was obtained, which
is also comparable to the NaHCO3 based electrolyte. Nonetheless,
TEM analysis of both samples demonstrated that these electrolytic
48 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54

Fig. 1. TEM micrographs of ZnO NPs electrosynthesized in the presence of 1 g/L PSS at 10 mA/cm2 and calcined at (a) 300 ◦ C, (b-c) at 600 ◦ C, and (d) their size distribution
histogram.

Fig. 2. TEM micrographs of electrosynthesized nanogels prepared with 1 g/L PSS in 30 mM NaHCO3 at different current density j: a) 1 mA/cm2 , b) 5 mA/cm2 , and c) 10 mA/cm2 .
 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54
Fig. 3. TEM micrographs of electrosynthesized nanogels prepared with 1 g/L PSS in different media at pH 8: a-a’) borate buffer, b-b’) 30 mM NaCl.
media influenced negatively the final particle morphology. Both
media promoted the formation, already in the as-prepared gel, of
rice-like microstructures (Fig. 3a-a’). Moreover, the presence of salt
crystals could not be avoided (Fig. 3b-b’). Therefore, it is assumed
that carbonate ions play an important role for the production of
nanostructured spheroidal particles, with reasonably narrow size
distribution, and the choice of NaHCO3 seemed to be the most
appropriate one.
3.1.3. Influence of temperature and stabilizer concentration
In several works involving hydrogen carbonate as electrolyte,
authors reported on the formation of various zinc hydroxides-
carbonates mixed species and complexes during zinc corrosion
[51,52,65,71]. In particular, it has been found that a main com-
ponent is a basic zinc carbonate Znx (CO3 )y (OH)z . The reaction
temperature was then raised to 80 ◦ C, in order to promote the direct
formation of the desired oxide [72]. However, IR characterization of
powders prepared at 80 ◦ C still showed the predominance of signals
associated to carbonate and hydroxide (Fig. S2).
The effect of PSS concentration was also tested employing 20 g/L
concentration of stabilizer in 30 mM NaHCO3 solution. This did not
49
cause any significant change in NPs chemical composition and size
as compared to lower concentration (Fig. 4a). On the other hand,
600 ◦ C-calcined NPs still showed the persistence of a relatively thick
organic layer around them, which could be a source of contamina-
tion due to byproducts of PSS degradation (Fig. 4b).
Considering the presented results, nanoparticles prepared at
j = 10 mA/cm2 with 1 g/L PSS in NaHCO3 30 mM at room temper-
ature were selected as optimal nanomaterial, which were then
characterized for further application in nanostructured organic-
inorganic OTFT active layers.
3.2. Spectroscopic characterization of ZnO NPs
Pristine and calcined samples were characterized by UV-Vis,
FTIR, and XPS spectroscopies to investigate their bulk and surface
chemistry, and the influence of thermal treatment on their com-
position. In Fig. 5, UV-Vis (panel A) and IR (panel B) spectra of the
prepared and calcined particles are presented.
The absorption band (␭max ) moved towards higher wavelengths
going from pristine particles (␭max = 349 nm) to ZnO nanomateri-
als annealed at 300 ◦ C (␭max = 361 nm) and 600 ◦ C (␭max = 373 nm).
50 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54
Fig. 4. TEM images of 600 ◦ C-calcined ZnO NPs electrochemically prepared with 20 g/L PSS in 30 mM NaHCO3 at 10 mA/cm2 . Panel b shows NPs surrounded by the PSS shell.
Fig. 5. Comparison of UV-Vis (A) and FTIR (B) spectra of pristine and calcined (at
300 ◦ C or 600 ◦ C) samples. In Fig. 5B, IR bands associated with main vibrations of
hydroxyl groups, carbonate moieties, and Zn-O bond are highlighted and labeled.
In pristine samples, the poor definition of the maximum could be
ascribed to the reduced presence of nanostructured ZnO. Moreover,
a second band at 262 nm was indicative of the presence of PSS,
which is hardly visible in the other two spectra. The red shift in NP
absorption band, which is generally attributed to an increase in NP
size [51], is in good agreement with TEM results as 600 ◦ C-calcined
ZnO NPs present a larger mean diameter (46 ± 8 nm) than at 300 ◦ C
(18.0 ± 1.1 nm). FTIR characterization allowed the investigation
of bulk chemical composition obtained after the electrosynthe-
sis (curve 1) and thermal treatment at 300 ◦ C (curve 2) or 600 ◦ C
(curve 3) for 1 h. Pristine particles mainly consist of hydrozincite
(Zn5 (CO3 )2 (OH)6 ) as IR bands associated to hydroxyl and carbon-
ate groups are clearly observable in agreement with literature
data [73]. In particular, the broad band at 3397 cm−1 (highlighted
in blue in Fig. 5B) is attributed to stretching vibrations of struc-
tural hydroxyl moieties and adsorbed water. Carbonate stretching
modes (highlighted in yellow in Fig. 5B) are also detected at 1510
and 1389 cm−1 (␯3 split frequency), 1045 cm−1 (␯1 ), 833 cm−1 (␯2 ),
and at 706 (␯4 ) [73]. However, it has been reported that hydroz-
incite can be decomposed at temperature above 250 ◦ C to form ZnO
[49,51,73], as confirmed by IR spectrum of 300 ◦ C-calcined samples,
which shows weak signals relevant to hydrozincite (␯3 split fre-
quency falling at 1510 and 1389 cm−1 ) and a single band around
450 cm−1 compatible with the Zn-O stretching mode. Complete
conversion to ZnO NPs can be achieved at 600 ◦ C as demonstrated
by the strong band at 413 cm−1 (red zone in Fig. 5B) with a shoulder
at 525 cm−1 (Fig. 5b, curve 3) [73]. Interestingly, the surface chem-
ical composition of pristine and calcined particles determined by
XPS (Table S1) led to similar results indicating that a low amount
of PSS is retained on ZnO NPs even after their treatment at 600 ◦ C
(see sulfur atomic%). Moreover, the analysis of Zn2p3/2 [63] and
ZnL3 M45 M45 regions showed that above 300 ◦ C, NPs are made of
ZnO. XPS data relevant to a commercial ZnO powder, to dried (at
70 ◦ C) electrosynthesized particles, and calcined NPs are summa-
rized in Table 2. Typical ZnL3 M45 M45 Auger region acquired on
600 ◦ C calcined ZnO NPs is reported in Fig. 6.
3.3. Use of ZnO NPs in OTFT electronic active layer
Calcined ZnO NPs were also applied to develop TFT based on an
organic-inorganic bilayer structure of P3HT and ZnO NPs under-
neath in place of a single mixed deposit P3HT/ZnO NPs [63]. Other
 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54 51

Table 2
Zn2p3/2 and Zn LMM peak positions, and Auger parameter (␣’) for commercial ZnO
powder, and nanoparticles prepared in this work.

Sample BEZn2p3/2 [eV] KEZnLMM [eV] ␣’ [eV]

ZnO STD 1021.7 ± 0.2 988.6 ± 0.2 2010.3 ± 0.2

Dried 70 ◦ C 1022.1 ± 0.2 987.5 ± 0.2 2009.6 ± 0.2
Calc. 300 ◦ C 1021.6 ± 0.2 988.5 ± 0.1 2010.1 ± 0.3
Calc. 600 ◦ C 1021.7 ± 0.1 988.5 ± 0.1 2010.2 ± 0.2

Fig. 6. Typical ZnL3 M45 M45 Auger signal of ZnO NPs calcined at 600 ◦ C.

studies [15,74–76] have already demonstrated that the implemen-

tation of ZnO NPs can change the properties of OTFT-based devices
in terms of improved performances and stability, which are closely
correlated to NP morphology, composition, etc. In this work, the
role of calcination temperature (i.e. 300 ◦ C and 600 ◦ C) and spin
coating speed of the ZnO NPs layer in the electrical performance of
the TFT device was investigated. Bare P3HT based OTFTs were also
tested for the sake of comparison. I-V transfer curves for all the
tested samples, plotted as (IDS )1/2 versus VG , are shown in Fig. 7.
ZnO NPs, used as inner layer, contributed to the improvement of
P3HT-based TFT figures of merit. In all cases, the bilayer structures
showed much higher drain current and mobility values from the
devices fabricated with bare P3HT. Such an occurrence can be tenta-
tively explained by the ability of ZnO NPs to reduce the trap density
√ high level of intermixing between the organic and inorganic phase.
Fig. 7. IDS vs VG plots for TFTs prepared using ZnO NPs calcined at different tem-
peratures (300 ◦ C or 600 ◦ C) and spin coated at two speeds (300 or 2000 rpm) prior
to P3HT deposition. A plot for bare P3HT TFT is presented for comparison.
Fig. 8. Output curves (A) and IDS vs VG plots (B) for TFTs based on bare P3HT and
P3HT/ZnO NPs.
in P3HT [74,77]. This is evident by the slight shift of the thresh-
old voltage towards more positive values in the case of the bilayer
structure (fig. 7), indicating a faster switch on of the devices incor-
porating the ZnO NPs layer underneath the organic semiconductor.
Furthermore, for the ZnO suspensions calcined at 300 ◦ C, the spin-
ning rate seems not to affect greatly the OTFT performance, whereas
a clear difference in the device performance occurs in the case of
600 ◦ C-calcined ZnO NPs upon changing the spinning conditions. In
particular, an improved performance was found for the suspensions
of 600 ◦ C-calcined ZnO NPs spun at 300 rpm. This behavior could be
related to the larger size and highest level of purity of the obtained
NPs calcined at 600 ◦ C, as shown by the morphological and spec-
troscopic characterization. Output (panel A) and transfer (panel B)
curves relevant to OTFT based on bare P3HT and on P3HT/ZnO NPs
(600 ◦ C/300 rpm) are compared in Fig. 8. Furthermore, the corre-
sponding extracted TFT characteristics, acquired in the saturation
regime, are presented in Table 3.
An enhancement of the drain current of more than 70% was
observed (Fig. 8). Moreover, the introduction of ZnO NPs under-
neath the organic semiconductor resulted in a one-order increase
of mobility (Table 3). Furthermore, in a relevant work reported by
Hammer et al. [78], the influence of Al doping in sol-gel processed
ZnO films under the P3HT layer was investigated. The improved
electrical performance of the hybrid TFT device was attributed to
It was suggested that the increase of surface roughness of the inter-
layer encouraged the infiltration of P3HT. This is in agreement with
52 R.A. Picca et al. / Electrochimica Acta 178 (2015) 45–54
Table 3
Characteristics of P3HT and P3HT/ZnO NPs TFTs.
Device ␮ [cm2 /Vs] ION /IOFF VT [V]
P3HT/ZnO NPs (5 ± 2)*10−3
12 ± 9 24 ± 7
Bare P3HT (7.2 ± 1.4)*10−4 23 ± 12 19.4 ± 1.1
previous observations of mobility enhancement due to infiltration
of P3HT on porous alumina dielectric. It was found that the mobil-
ity increased with the increase of the pore diameter in alumina.
Based on simulations, it was shown that the hole concentration
was greater in the polymer region surrounded by the dielectric that
in the neat P3HT film [79]. It was also hypothesized that a better
alignment of the polymer chains is obtained in this case. Morpho-
logical and structural characteristics affect greatly the performance
of the organic semiconductor [80,81]. On the other hand, in Table 3
no significant differences in ION /IOFF could be assessed between the
two classes of devices. It is worth mentioning that only a p-type
behavior could be seen on both transistors. No ambipolar behav-
ior could be observed for ZnO-modified OFETs, probably due to the
deposited ZnO NP coating not reaching the limited inter-particle
connection [82].
4. Conclusions
In summary, we proposed a green electrochemical synthesis
strategy of ZnO NPs in aqueous alkaline media with low-cost
non-toxic chemicals at mild conditions. The most appropriate mor-
phology and composition of ZnO NPs could be achieved by selecting
a suitable anionic stabilizer (PSS) at an optimized concentra-
tion (1 g/L), as well as by suitable electrochemical (j = 10 mA/cm2 )
and annealing conditions (600 ◦ C for 1 h). Compared to previ-
ously reported methods (e.g. EDOC syntheses), the ZnO NP yield
was considerably higher. A detailed spectroscopic characterization
revealed the relevance of the annealing step for ensuring com-
plete conversion of gels made from mixed hydroxide-carbonate
species into nanostructured zinc oxide. Moreover, ZnO NPs could
be readily implemented as additional layer deposited underneath
a P3HT organic semiconductor film by spin coating for developing
bilayer OFETs with enhanced unipolar mobility, as compared to sin-
gle P3HT devices. Different NP loadings will be further considered
to investigate possible improvements of the device performance,
also in terms of ambipolar behavior. Moreover, owing to the low
toxicity, and biocompatibility of ZnO NPs, current work is focused
on the use of the ZnO interlayer as suitable matrix for the imple-
mentation of biomolecules using the proposed OTFT structures for
biosensing applications.
Acknowledgements
This paper is dedicated to professor Pier Giorgio Zambonin on
the occasion of his 80th birthday.
LT and NC gratefully acknowledge “PON SISTEMA” (Ital-
ian Ministry of University and Research, contract number
PONa3 00369 titled “Laboratorio per lo Sviluppo Integrato delle
Scienze e delle TEcnologie dei Materiali Avanzati e per disposi-
tivi innovativi–Laboratorio SISTEMA-”) and “OFET biosensors for
point-of-care applications–sense-of-care” (FP7-People-ITN-EID-
2012 under Grant Agreement 316845) projects for partial financial
support of this work.
DH, CK, and BM acknowledge a fellowship by Erasmus
SMP/DAAD and the Analytical Division of the GDCh for a research
stay of DH at the Università degli Studi di Bari “Aldo Moro”.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.electacta.2015.
07.122
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