Accepted Manuscript

Title: Impact of surfactants covering ZnO nanoparticles on

solution-processed field-effect transistors: From dispersion
state to solid state

Author: A.K. Diallo M. Gaceur S. Ben Dkhil Y. Didane O.

Margeat J. Ackermann C. Videlot-Ackermann

PII: S0927-7757(16)30268-0
DOI: http://dx.doi.org/doi:10.1016/j.colsurfa.2016.04.036
Reference: COLSUA 20593

To appear in: Colloids and Surfaces A: Physicochem. Eng. Aspects

Received date: 1-3-2016

Revised date: 12-4-2016
Accepted date: 13-4-2016

Please cite this article as: A.K.Diallo, M.Gaceur, S.Ben Dkhil, Y.Didane,
O.Margeat, J.Ackermann, C.Videlot-Ackermann, Impact of surfactants covering ZnO
nanoparticles on solution-processed field-effect transistors: From dispersion state
to solid state, Colloids and Surfaces A: Physicochemical and Engineering Aspects
http://dx.doi.org/10.1016/j.colsurfa.2016.04.036

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Impact of surfactants covering ZnO nanoparticles on solution-processed
field-effect transistors: from dispersion state to solid state

A.K. Diallo, M. Gaceur, S. Ben Dkhil, Y. Didane, O. Margeat*, J. Ackermann, C. Videlot-

Ackermann*.

Aix Marseille Université, CINaM, UMR CNRS 7325, 13288, Marseille, France.

[*] Corresponding Authors:

E-mail address: margeat@cinam.univ-mrs.fr (O. Margeat)
videlot@cinam.univ-mrs.fr (C. Videlot-Ackermann)

Graphical abstract

Highlights

 Impact of surfactants covering ZnO nanoparticles

 Impact of dispersion state and solid state on transport performance
 Modification of the surface of particles and the resulting particle-particle interaction in
thin films
 Low-temperature operating nanoparticulate ZnO TFTs

1
Abstract

Solution-processed n-channel oxide semiconductor thin-film transistors (TFTs) were fabricated

using zinc oxide (ZnO) nanoparticles. The solution-processable semiconductor dispersions
based on ZnO were prepared by dispersing the synthesized ZnO nanospheres in solution. The
dispersion state was strongly affected by either the surfactant type or the solvent nature. Two
small organic molecules commercially available, ethanolamine (EA) and benzoic acid (BA),
were used as surfactant in alcohol solvent. The introduction of EA reduced the size of
nanocrystal agglomerates and improved their dispersion properties simultaneously. Spin-
coating of EA-modified ZnO dispersion following by a low-temperature annealing produced
uniform polycrystalline nanoparticulate thin films. The resulting solid state of thin films
demonstrated that the incorporation of EA has not a direct impact on the morphology but
slightly decrease the field-effect mobility by less than one order of magnitude due to the
insulating properties of EA organic molecules grafted on ZnO particles. As contrary, BA
generated the existence of large-size cohesive ZnO agglomerates in solution which persist in
the solid state to generate a less efficient charge transport. The modification of the particles
surface by capping agent and the resulting particle-particle interactions in thin films were
attributed as the main factors to impact on the field-effect mobility. To surfactant-free
dispersions, the cohesive forces in ZnO agglomerates have been strongly influence by the
solvent nature for a balance between a suitable dispersity of solution state and an effective solid
state to transport of charges.

Keywords: ZnO nanoparticles, dispersion state, thin solid film, transistor, particle-particle
interaction.

1. Introduction

Large varieties of nanoparticulate inorganic semiconductors were synthesized during the last
two decades and applied as “building blocks” for solution-processed devices [1]. The ability of
solution processes to easily mix and match nanomaterials with different compositions and
dimensions should be explored to greater extent regarding new opportunities for improving
properties and performances of resulting materials. Among semiconducting metal oxides,
solution-processed zinc oxide (ZnO) is one of the most promising n-type semiconductor
materials thanks to its efficient electron mobility, environmental stability combined with optical
transparency due to a direct wide band-gap of approximately 3.3 eV at room temperature [2,3].

2
Among many fabrication methods employed to prepare ZnO nanoparticles (NPs), including
sol-gel processes [4-6], vapor phase synthesis [7], simple solution combusting [8], and spray
pyrolysis [9], these methods generally require complex equipment and complicated operational
procedures; therefore, the nano-crystals synthesis in solution offers a simple route for the
synthesis of metal oxide NPs in high yield. This solution-based method is relatively simple and
convenient, very cheap and facile, environmentally friendly, and can provide the resulting NP
solutions in a pure and well-dispersed form under atmospheric conditions. Coupling to the spin-
coating process, these NP solutions are processable at low temperature (< 150°C) to form high-
quality, continuous films free from cracks and pinholes to be compatible with flexible electronic
applications. Because the two main processes, the nano-crystal synthesis and the layer
formation made by spin-coating are essentially independent, such procedure has great
advantages. Additionally, the nano-crystal synthesis offers a fine control of the final dispersion
which can be stable for hundreds of hours without precipitation with the use of surfactants.
Much efforts have been applied toward the development of solution-based fabrication processes
for ZnO thin films involved in devices as thin film transistors (TFTs) [10-16]. More recently,
solution processed ZnO layers by spin-coating have been successfully applied as interfacial
layers (ILs) sandwiching the photoactive layer in solution-processed organic solar cells [17-
21]. ILs in organic solar cells are of great interest because of their different tasks such as the
improvement of the light absorption within the photoactive layer, improvement of the charge
carrier extraction towards the electrodes and to avoid charge carrier recombination at the
interfaces. Bandgap engineering at the interface between inorganic and organic semiconductors
is crucial for highly efficient solar cells. A simple polar co-solvents treatment with 2-
methoxyethanol (2-Me) and ethanolamine (EA) on ZnO layers has shown a reduction of the
energy barrier between the conduction band of ZnO and the low unoccupied molecular orbital
(LUMO) of the acceptor in the active layer [17]. To determine the influence of EA as direct
capping agent on NPs, such molecule was introduced in ZnO NP dispersions. As observed in
previous studies based on ZnO NPs, EA has led to agglomerate-free dispersions [18, 21]. Such
stabilized surfactant dispersions have allowed the processing of ZnO optical spacer layer with
improved morphology as well as improved contact resistance compared to untreated ZnO [21].
Even with a minimal addition, such surfactants were present on the particles surface in the solid
state and can introduce a barrier for charge transport between the particles. Consequently,
solution processable semiconductor materials suffer of a specific dilemma between the
necessity of effective colloidal stabilization of NPs and effective charge transport [22]. On one
hand, NPs must be dispersible in a solvent to form aggregate-free dispersion state. On the other

3
hand, surfactants and other organic materials being used to synthesize and/or disperse
nanocrystals can introduce a barrier for charge transport between particles in solid state. The
use of such coating for optoelectronic applications must be well-chosen in terms of chemical
structure, physicochemical properties and concentration.

The purpose of the present paper is to highlight the significance of surfactants in ZnO
dispersions intended to form the transporting layer in solution-processed TFTs. Two different
types of commercially available surfactant, i.e. EA and benzoic acid (BA), were used in alcohol
solvent. The selection was voluntary focused on small organic molecules. EA is a classic
stabilization agent widely used in conventional metal salt solution, because of its excellent
metallic chelating activity [23]. The molecule is both a primary amine and a primary alcohol
(due to a hydroxyl group) linked by an insulating carbon chain. BA is a simple aromatic
carboxylic acid which can be grafted on metal oxides together with a cyclic continuous π bond
between the carbon atoms (Figure 1a). Impact on charge transport was studied in solution-
processed n-channel oxide semiconductor TFTs. Polycrystalline nanoparticle-based thin films
were produced by spin-coating ZnO dispersions following by a post-annealing at low-
temperature ( 150°C). Depending on surfactant, the dispersion state presented either isolated
NPs or agglomerates. The resulting thin films demonstrated that the incorporation of EA has
not a direct impact on the morphology compare to untreated NPs but slightly decrease the field-
effect mobility. As contrary to EA, the use of BA as surfactant has generated the existence of
large-size cohesive agglomerates of ZnO in both suspension and solid states unfavourable to
efficient charge transport. The formulation of surfactant-free dispersions was also investigated
as function of solvent. By analysing the variation of the field-effect mobility vs. surfactant type
and solvent nature, the modification of particles surface and the resulting particle-particle
interaction in thin films were attributed as the limiting factors to electron transfer by tunnelling
at particle-particle junctions.

2. Experimental

Solutions preparation. The ZnO NPs were prepared following the procedure described
previously [24] according to the well-known route introduced by Pacholski [25] and Sirringhaus
[11]. The solution-processable n-type semiconductor dispersions based on ZnO were prepared
by transferring the synthesized ZnO nanospheres from methanol solutions to isopropanol or

4
chloroform at 30 mg/mL. ZnO NPs with an average diameter of 6 nm were formed as shown in
Figure 1a [21]. As surfactant, two different types of commercially available molecules, i.e.
ethanolamine (EA) and benzoic acid (BA), were used (Figure 1a). In isopropanol dispersions,
a fraction of EA was added and the amount was specified by its ratio with respect to the net
mass of ZnO, for instance 0.2 vol% represents 0.2 µL in 1 mg/mL of ZnO in isopropanol. The
ratio of surfactant ranged from 0.05 to 1 vol.%. After mixing of EA and ZnO in isopropanol,
small optical changes of the ZnO solution were visible already seconds after the introduction
of EA due to the spontaneous grafting of EA on the surface of ZnO. However, ultrasonic
treatment was applied for 10 min, during which solubility of the ZnO NPs was gradually
increased until isolated NPs were obtained in isopropanol. To study the influence of surfactant,
BA was added to isopropanol dispersion with a ratio equivalent to 0.2 vol.%. As references
surfactant-free ZnO dispersions were prepared in isopropanol and in chloroform. Size
distribution of the NPs within the solutions was determined with Dynamic Light Scattering
methods (DLS) using a NanoZetaSizer from Malvern.

Thin film transistors fabrication and characterization. The obtained dispersions were spin-
coated on TFT architectures. A schematic representation and a top view image are shown in
Figures 1b and 1c, respectively. Interdigitated source and drain electrodes structured by a lift-
off technique were deposited on n-doped silicon wafers covered with thermally grown silicon
dioxide (SiO2). Interdigitated electrodes were formed by 30 nm of gold (Au) and 10 nm of an
adhesion layer of indium tin oxide (ITO). Such interdigitated TFT structures were purchased
from Fraunhofer (Germany) with a channel width W of 10 mm and different channel lengths L
ranging from 2.5, 5, 10 and 20 µm. The capacitance per unit area of 230 nm thick SiO2 dielectric
layers was 14.610-9 F.cm-2. Prior the deposition of NPs, the substrates were consecutively
cleaned by sonication with acetone, ethanol and rinsed with deionized water. The SiO2
substrates were then dried and treated with final UV-ozone plasma for 15 min. Trimethylsilation
of the Si/SiO2 surface was carried out by dipping the silicon wafers to hexamethyldisilazane
(HMDS) solution at room temperature in a closed container for one night. The capacitance per
unit area of HMDS-treated dielectric layers was 910-9 F.cm-2. HMDS-treatment is well known
to provide an uniform hydrophobicity over the entire substrate surface while removing various
electron traps present on silicon oxide surface [26,27]. Spin-coating was performed using a
spin-coater machine from SET Company (model TP 6000) where time, speed of the run were
fixed to 30 sec. and 2000 rpm/min, respectively. Dispersions were spin-coated directly after an
ultrasonic treatment during 10 min. After the solution deposition on top of the source and drain

5
electrodes, the coated substrates were annealed on a preheated hot plate (80°C, 150°C or 300°C)
for 30 min as a thermal post-treatment. With a boiling point (Tbp) of 61.3°C for chloroform and
82.6°C for isopropanol, solvents were completely evaporated for temperature reaching 150°C,
but the surfactants remained adsorbed on the surface of ZnO. Only for a post-annealing at
300°C, surfactants (Tbp = 170°C for EA and 249.2°C for BA) and solvents were completely
removed. Spin-coating and annealing were performed in a nitrogen-filled glove box. Current-
voltage characteristics were performed with a Hewlett-Packard 4140B pico-amperemeter-DC
voltage source. The mobility values µ were extracted from the saturation region of the transfer
curves with the equation:

Id = (W/2L) Ciµ (Vg-Vt)2 (1)

where Id is the drain-source voltage, Ci is the capacitance per unit area of the gate insulator layer
(Ci = 910-9 F.cm-2), Vg is the gate voltage, Vt is the threshold voltage, and µ is the field-effect
mobility. All electrical characterization results were performed in nitrogen-filled glove box.

Thin films characterization. Morphological study of ZnO NPs was carried out by the high-
resolution transmission electron microscope (HR-TEM) JEOL 3010, where samples were
prepared by drop casting of diluted solution on a mesh-coated carbon film. Microstructure of
thin films has been investigated using a scanning electron microscope (JEOL JSM 6320F). SEM
micrographs were made both on top and cross sections on NPs-based thin films deposited on
silicon substrates covered with 300 nm thick SiO2 dielectric layers. XRD measurements were
realized using a Rigaku RU200-2BH, rotating anode (operating power 50 kV-30 mA) equipped
with a Xenocs Fox 3D Cu 12-INF optics and a Mar345 Image Plate Detector. The X-Ray beam
(11 mm2) arrived on the samples at an incidence angle of about 12 degrees. In order to get a
good signal to noise ratio, thicker ZnO layers were used. This was achieved by depositing the
NPs dispersions five times by spin-coating. The samples were heated to the corresponding
temperature (80, 150 or 300°C) after the final spin-coating step.

3. Results and discussion

In order to evaluate the electron mobility in ZnO layers, we fabricated TFTs with a bottom gate
and bottom contact structure, as illustrated in Figures 1b and 1c, with ZnO active layers
deposited by spin-coating. The implementation and characterization of solution-processed
field-effect transistor devices require both the preparation of inks, i.e. dispersion state, and their
6
deposit in thin layer, i.e. solid state. The resulting solid thin film can be therefore directly related
to the ink formulation. Dispersion state of solutions is well-known to depend on various
parameters as nature, concentration and geometrical structure of NPs, nature of solvent,
presence or not of surfactants, as well as chemical structure and concentration of such
surfactants. Resulting solid state will depend not only on these chemical parameters but also on
physical parameters such as deposition technique, substrate, thermal post-treatment, etc.

3.1 Impact of surfactants on solution state

ZnO solutions without visible aggregates were previously observed in isopropanol by using EA
(0.2 vol.%) as surfactant [23]. Based on such previous results, ZnO dispersions at 30 mg/mL in
isopropanol mixed with different volume ratio (0.05 to 1 vol.%) of EA have been prepared in
the present study. ZnO transporting layers were realized by spin-coating of prepared dispersions
on interdigitated TFT structures. To determine the influence of surfactant, a reference ZnO
dispersion without EA (pristine ZnO dispersion) was also prepared. While Figure 2 shows the
ZnO dispersions, representative hydrodynamic size of ZnO NPs are summarized in Table 1.
Dynamic light scattering (DLS) measurements reveal that ZnO NPs without EA modification
form agglomerates of 61.2 nm in diameter, and thus much larger than the single particle
diameter of 6 nm as obtained from HR-TEM analysis (Figure 1a). By adding 0.2 or 1 vol.% of
EA as surfactant, the DLS value drops to 7-8 nm indicating the existence of agglomerate-free
dispersions. Due to the size of ZnO agglomerates, the pristine ZnO dispersion presents a weak
milky white aspect. By adding EA to ZnO in isopropanol, small optical changes of ZnO solution
were visible already seconds after the introduction of EA due to the spontaneous grafting of EA
on the surface of ZnO to enhance the metal species solubility. However in order to produce
visible agglomerate-free solutions, ultrasonic treatment was applied during 10 min to gradually
reduce the agglomerates size after EA treatment. Importantly, the EA-modified dispersion was
stable over a month without occurrence of any NPs aggregation, as visually observed and
confirmed by regular DLS measurements. A strong milky white aspect was reached by
changing the surfactant from EA to BA (Figure 2). Such milky aspect results from a stronger
scattering of incident light. Even for lower concentrated dispersions (< 30 mg/mL), no DLS
measurement was possible proving the persistent existence in solution of large-size cohesive
agglomerates of BA-treated ZnO. Unlike EA, BA molecules as capping agent lead to an
agglomeration of ZnO NPs in solution. It is obvious that surfactants modify the particle surface
to control their interactions in solution to form either isolated NPs or agglomerates.

7
3.2 Impact of surfactants on solid state

In order to evaluate the impact of surfactants on electron mobility in ZnO transporting layers,
solution-processed TFT devices were realized and characterized. The output characteristics for
different gate-source voltages (Vg) were measured for pristine and modified ZnO TFTs.
Deposition process and electrical measurements were both performed in nitrogen-filled glove
box. Transistor activity was observed for ZnO TFTs by application of positive drain and gate
voltages (see Figure 3) demonstrating that ZnO behaves as n-type semiconductor independently
of the presence of surfactant. While TFTs for pristine ZnO present an ohmic-like behaviour
with a quasi-linear relationship between the current and the voltage (Figure 3a), TFTs with EA-
treated ZnO show saturation in enhancement mode by applying a positive gate field as
exemplarily shown in Figure 3b for 0.2 vol.% of EA. The field-effect mobility (µ), the threshold
voltage (Vt) and the on/off ratio (Ion/Ioff) of ZnO TFTs are summarized in Table 2 as function
of surfactant and temperature annealing. Thin films were post-annealed at 80°C or 150°C for
30 min after spin-coating process. XRD diffraction patterns of corresponding spin-coated thin
films are identical and subsequently independent of the post-annealing temperature (Figure 4).
All diffraction peaks were well matched accordingly with hexagonal-wurtzite-structure ZnO
peaks [28]. Figure 5 gives the electron mobility dependence versus the volume ratio (vol.%) of
EA in ZnO dispersions at 30 mg/mL in isopropanol. From equation (1), a saturation electron
mobility up to 8.510-6 cm2/Vs was extracted for spin-coated thin films from pristine ZnO
suspension in isopropanol and post-annealed at 80°C. Lower mobility values down to 210-6
cm2/Vs were systematically obtained for surfactant containing suspensions. An identical
mobility value between 0.2 and 1 vol.% EA demonstrates that further addition of EA has not
impact on the charge transport process at low-temperature process. Although the ZnO surface
modification by EA is of great impact to obtain well-dispersed NPs in solution, the persistent
presence of such surfactant in thin films annealed at 80°C induces reduced electron mobility
values. Average higher mobility values were obtained after a thermal post-treatment at 150°C
for 30 min (Figure 5) mainly due to a reorganization energy supplied to the particles during the
complete evaporation of solvent to form denser thin films as observed in the following SEM
analysis. However, lower mobility values were systematically observed for EA-treated ZnO
NPs compared to pristine ZnO. With a maximum value at 0.2 vol.% for a thermal treatment at
150°C, such volume ratio of EA represents the well-adjusted amount to obtain isolated NPs in
solution state together with minimized disruption on charge transport in solid state for low-
8
temperature fabrication of ZnO TFTs. For annealing temperature lower to 170°C,
corresponding to the boiling point of EA, surfactant molecules around ZnO surface still induce
local tunneling barriers between particle-particle junctions. The percolation pathway of
electrons is altered by the presence of EA and the mobility of electrons is subsequently reduced.
By increasing the post-annealing temperature to 300°C, both surfactant and solvent were
completely removed (see Figure S2 and S3 for details) and the impact of surfactant is no longer
active.
SEM analyses of spin-coated ZnO thin films from NP dispersions in isopropanol highlight a
comparable morphology of films independently of EA concentration and temperature
annealing, as seen in Figure 6. Uniform and densely packed films were obtained on a large scale
i.e. tens of microns. Introducing EA as surfactant reduces the size of agglomerates in dispersion
state without a direct impact on solid state. Critical parameters of TFTs fabrication prepared
with nano-crystals are the layer quality at the interface and the morphology of the layers. An
attentive look at the cross-sectional SEM images (Figure S4) indicates that the roughness at the
interface with SiO2 is low. The alignment plane of NPs and of their agglomerates is defined by
the flat surface of the substrate. The only difference noted is the average smaller thickness of
ZnO thin films from dispersion containing EA (Table S1). Such resulting thinner films can be
assigned to a lower viscosity of dispersions based on EA-treated ZnO vs. pristine ZnO. A low
interface roughness independently of EA surfactant concentration and temperature annealing
indicates that comparable geometrical traps for the carriers will be involved in either EA-treated
ZnO or pristine ZnO layers [15]. While the morphology of thin films was one of the main
parameters influenced by polymeric stabilizer incorporated in ZnO dispersion [14], the use of
a small molecule as EA has not a direct impact on the nanoscale assembly. Lower thicknesses
for thin films post-annealed at 150°C (see Table S1) highlight the formation of denser
nanoparticulate ZnO films thus resulting in a higher contact between NPs. The variation of
mobility values, decreased by incorporation of EA and increased with temperature annealing,
is consequently caused by the surface state of the ZnO NPs to ensure the junction between them.
With a boiling point (Tbp) at 82.6°C for isopropanol, solvent is completely evaporated for
temperature reaching 150°C, but the surfactant remains adsorbed on the surface of ZnO. The
decreased of mobility values at 80°C and 150°C by covering ZnO NPs with EA surfactant is
due to the insulating properties of EA molecules.
By changing the surfactant to BA, the current and the mobility have decreased by more than
one order of magnitude (Figure 3c). Such decrease can been assigned directly to the
morphology of thin films where an incompletely coated surface with high circular formations

9
was observed (Figure S5). These domains on the substrate were the result of the existence of
large agglomerates in ZnO suspensions with 0.2 vol.% of BA. The cohesive forces inside these
agglomerates persist during the spin-coating process. BA used as surfactant in ZnO dispersions
is consequently no suitable to promote a packed NPs layer and an efficient charge transport in
solid state.

3.3 Impact of solvent towards surfactant-free dispersion for efficient transport

For barrier-free contacts between particles, ZnO suspensions at 30 mg/mL were prepared in
different solvents, i.e. chloroform, tetrahydrofurane and chlorobenzene, without the
introduction of surfactant. Dispersions were spin-coated on TFT structures followed by a
thermal post-treatment at 80°C for 30 min to form the active layers. No charge transport was
observed for thin films based on ZnO NPs in chlorobenzene probably due to the high boiling
point (Tbp = 132°C) of the solvent compared to the low applied annealing temperature. TFTs
based on ZnO NPs from chloroform (Tbp = 62°C) and tetrahydrofurane (Tbp = 66°C) dispersions
delivered electron mobilities around 10-6 and 10-7 cm2/Vs, respectively. Mobility values up to
3-510-6 cm2/Vs were measured for thin films obtained by spin-coating from ZnO NPs in
chloroform (Figure 3d and Table 2). Importantly, these mobility values are even higher than
ones obtained for EA-treated ZnO in isopropanol post-annealed at 80°C. Surfactant-free ZnO
NPs form transparent solutions in chloroform with a weak milky white aspect (Figure 2) even
after an ultrasonic treatment applied during 10 min. DLS measurement reveals that ZnO NPs
in chloroform form agglomerates of 63 nm in diameter (Table 1), and thus equivalent to
agglomerates in isopropanol without EA modification. XRD diffraction patterns of
corresponding spin-coated thin films were identical and subsequently independent of the
solvent (Figure S6). By changing the solvent from isopropanol to chloroform, the use of
surfactant is consequently abolished to achieve low-temperature-grown ZnO films with
comparable electrical characteristics. Despite large agglomerates in solution (63 nm), Figure 7
shows the uniformity of the surface for both spin-coated ZnO thin films post-annealed at 80°C
and 150°C. Only small agglomerates, with diameters of 15-25 nm, uniformly and densely
dispersed on the surface were formed. Such small ZnO agglomerates are densely side by side
packed with an actual film thickness of 75 nm for a post-annealing at 80°C (Figure S7). Thus
it can be concluded that although ZnO agglomerates in chloroform were ten times larger than
ones for EA-treated ZnO in isopropanol, their presence in dispersion state does not rule out the
formation of homogeneous layers in solid state for an efficient charge transport.
10
4. Conclusion

Solution-processed n-channel oxide semiconductor TFTs were fabricated using ZnO

nanoparticles. The impact of either surfactant or solvent on performances of low-temperature
nanoparticulate ZnO TFTs was systematically investigated on both dispersion and solid states.
Two different types of small organic molecules, i.e. ethanolamine and benzoic acid, were used
as surfactants. Low-temperature operating nanoparticulate ZnO TFTs require (i) a sufficient
degree of nanoparticles dispersity in solvent with low cohesive forces of agglomerates to form
uniform and densely-packed films by spin-coating, (ii) a well-adapted modification of particles
surface to provide an efficient particle-particle interaction in thin films and (iii) a low interface
roughness. The present work clearly demonstrated that the dilemma between the dispersion
state and the solid state has to be considered for efficient solution-processed devices as not only
chemical parameters but also physical parameters influence the final efficiency.

Acknowledgements

The authors thank for funding SFUMATO project (Fonds Unique Interministériel) and
SUNFLOWER project (FP7-ICT-2011-7). The authors are grateful to Damien Chaudanson and
Vasile Heresanu from CINaM (UMR CNRS 7325) for assistance in SEM and in X-ray
diffraction measurements.

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Figure captions

Figure 1: (a) TEM images of ZnO nanospheres and chemical structure of surfactants. (b)
Schematic device structure of ZnO-based transistors. (c) Optical microscopy image of
interdigital structures used for transistor application.

14
Figure 2: Optical images of solutions based on ZnO nanoparticles in isopropanol at 30 mg/mL
without surfactant (pristine ZnO), with 0.2 vol.% of EA, with 1 vol.% of EA and with 0.2 vol.%
of BA, compare to ZnO nanoparticles in chloroform at 30 mg/mL without surfactant (pristine
ZnO).

Figure 3: Output characteristics of TFT based on ZnO in isopropanol (iso) without surfactant
(pristine ZnO) (a), with 0.2 vol.% of EA (b), with 0.2 vol.% of BA (c) and in chloroform
(CHCl3) without surfactant (pristine ZnO) (d). Thin films were made by spin-coating of
dispersions following by a thermal treatment at 150°C for 30 min.

15
Figure 4: XRD diffraction patterns of spin-coated thin films based on ZnO nanoparticles in
isopropanol with 0.2 vol.% of EA. Thin films were post-annealed at 80°C (thick line) or 150°C
(thin line) for 30 min.

16
Figure 5: Electron mobility dependence versus the volume (vol.%) of ethanolamine (EA) as
surfactant added to ZnO inks at 30 mg/mL in isopropanol. Thin films were made by spin-
coating of dispersions containing different fraction of surfactant following by a thermal
treatment at 80°C or 150°C for 30 min.

17
Figure 6: SEM images of spin-coated ZnO thin films from isopropanol solutions at 30 mg/mL
containing different fraction of surfactant (0, 0.2 or 1 vol.% of EA) following by a thermal
treatment at 80°C or 150°C for 30 min. Scale bar: 100 nm.

Figure 7: SEM images of spin-coated ZnO thin films from chloroform solution at 30 mg/mL
following by a thermal treatment at 80°C (a) or 150°C (b) for 30 min. Scale bar: 100 nm.

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Table 1: Hydrodynamic size of ZnO nanoparticles vs. solvent and surfactant from solutions at
30 mg/mL.

Hydrodynamic
Solvent
size (nm)
Isopropanol 61.2
Isopropanol+
7
0.2 vol.% EA
Isopropanol+
8.1
1 vol.% EA
Isopropanol+
-*
0.2 vol.% BA
Chloroform 63
*no usable data.

Table 2: TFT data of spin-coated ZnO thin films from solutions at 30 mg/mL vs. vol.% of
surfactants (EA or BA) and solvent (isopropanol or chloroform). Thin films were annealed at
80 or 150°C for 30 min after the spin-coating process.

Post-
Surfactant
Solvent annealing µ (cm2.V-1.s-1) Vt (V) Ion/Ioff
(vol.%)
temperature
w/o* 80°C 6.3-8.510-6 (-3)-(+8) 0.9-3.2104
150°C 2.3-2.510-5 (-4)-(+3) 0.9-2.2105
80°C 2.1-3.110-6 (-1.5)-(+2.5) 0.4-7.2103
0.05 of EA (+1.3)-
150°C 4-510-6 0.3-2.2104
(+4.2)
0.1 of EA 150°C 5.8-610-6 (-0.5)-(+1.4) 0.7-6.7105
Isopropanol 80°C 1.8-2.110-6 (-3)-(+0.4) 7.9-8.6103
0.2 of EA
150°C 5.7-710-6 (-0.1)-(+2.4) 0.5-7.3105
0.5 of EA 150°C 4.8-5.610-6 (+3.8)-(+6) 5.5-6.5104
80°C 2-2.210-6 (-0.5)-(+0.4) 8.7-9.9103
1 of EA
150°C 1.1-2.810-6 (-6)-(+25) 7.2-8.5104
80°C 1.7-1.910-7 (-7)-(-3) 0.7-1.7103
0.2 of BA
150°C 1.1-1.310-7 (+1)-(+3) 2.5-6.2102
80°C 3-510-6 (+18)-(+20) 0.3-4106
w/o* Chloroform
150°C 1.4-2.110-4 (+5)-(+9) 0.5-2107
w/o* ZnO solutions without surfactant (pristine ZnO)

19