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available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/carbon

Impact of ink formulation on carbon nanotube network

organization within inkjet printed conductive films
Aurore Denneulin

a,b

, Julien Bras b, Fiona Carcone

a,b

, Charles Neuman a, Anne Blayo

b,*

Polypore, 27-41, bd Louise Michel, F-92230, Gennevilliers, France

Laboratory of Pulp and Paper Science and Graphic Arts (LGP2), Grenoble Institute of Technology (INP Grenoble - PAGORA),
461 Rue de la Papeterie, BP 65, 38402 St Martin dHe`res, France

A R T I C L E I N F O

A B S T R A C T

Article history:

The inkjet printing of an aqueous suspension of carboxylic acid-functionalized single

Received 28 July 2010

walled carbon nanotubes (SWCNT-COOH) and of a conductive ink combining SWCNT-

Accepted 6 February 2011

COOH with the conductive polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT-PSS) was studied. A dimensionless study predicted the behavior
of these two fluids in a given printing system. Observations at different scales were performed on the printed samples to visualize the arrangement of the carbon nanotube
(CNT) network within the printed layer. An innovative way to localize CNTs within the
printed patterns was developed by using a mapping technique of surface sample, based
on a scanning electron microscope coupled with an energy dispersive X-ray spectroscope.
The SWCNT-COOH aqueous suspension is subject to the halo (or coffee ring) effect,
which is a well-known phenomenon in inkjet printing, whereas the SWCNT-COOH/
PEDOT-PSS ink offers a more homogeneous CNT network. The CNT orientation has also
been under investigation. For the SWCNT-COOH suspension, specific orientations of the
CNTs were recorded, whereas for the SWCNT-COOH/PEDOT-PSS ink, a more homogeneous
CNT distribution with a random orientation was obtained. This study proved also that the
droplet ejection velocity can have an impact on the CNT distribution and consequently on
the electrical performances of the ink.
 2011 Elsevier Ltd. All rights reserved.

1.

Introduction

Carbon nanotubes (CNTs) have drawn considerable attention

in the last decade due to their nanometer size, their unique
quasi one dimensional structure and their electrical,
mechanical, and thermal properties [14]. Indeed, the intrinsic electrical resistivity of CNTs was found to be approximately as low as 106 X m. Random networks of CNTs
provide an unusual type of electronic material that can be
integrated into electronic devices by several methods (printing processes [5], airbrushing [6], solvent evaporation [7,8],

spin coating [9], bar coating [10]). The electrical properties

of such materials make them attractive for numerous applications in electronics. However, as already demonstrated
[11], the stability of CNT suspensions is difficult to achieve
because the nanoparticles tend to aggregate easily due to
their high van der Waals attraction [12,13]. Working with
covalent functionalized carbon nanotubes is now considered
as a good compromise [11]. Indeed, the functionalization
strongly facilitates the separation of nanotube bundles into
individual tubes, which allows obtaining a stable dispersion
of CNTs in aqueous solvent [10,11,14,15]. In a recent study

* Corresponding author: Fax: +33 0 476 826 933.

E-mail addresses: aurore.denneulin@free.fr (A. Denneulin), Anne.Blayo@grenoble-inp.fr (A. Blayo).
0008-6223/$ - see front matter  2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2011.02.012

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of our research group, a method to prepare a conductive ink

based on carboxylic acid-functionalized single walled carbon
nanotubes (SWCNT-COOH) and on the conductive polymer
poly(3,4-ethylenedioxythiophene) doped with poly(styrene
sulfonic acid) (PEDOT-PSS) was described [11]. In this conductive ink, SWCNT-COOH is homogeneously dispersed within
the matrix. However, the conductivity of this ink is lower
than the intrinsic conductivity of CNTs. This phenomenon
is due to the numerous contact resistances between CNTs,
which are organized in a complex network. Up to now,
knowledge about CNT network observed on the large-scale
is very limited [16,17], but is essential for understanding
and improving the electrical properties. The main issue is
that there is no possibility to observe nano-elements at a
micrometer scale. Indeed, only very located zone can be
observed at nanoscale thanks to scanning and transmission
electron microscopy (SEM, TEM) [11,18,19], and atomic force
microscopy (AFM) [20,21]. On the contrary, on a micrometer
zone, it is almost impossible to visualize individual nanoparticles. Therefore, in order to analyse CNT distribution within
printed patterns, one challenge of this paper was to propose
an innovative protocol, offering a compromise between optical and scanning electron microscopy, by using a SEM coupled with an energy dispersive X-ray spectroscope (EDS).
Thanks to this method, carbon mapping of the printed samples can be obtained.
Among different processes of CNT suspension deposition,
inkjet printing appears as a promising one, on account of its
ability to precisely deposit picoliter volumes to a pre-determined position onto a wide range of substrates. Several reviews dealing with new applications of inkjet printing are
now available [2224]. Moreover, the demand for nanoparticle inkjet inks (mainly nanoparticles metallic inks) is growing from day to day for various kinds of applications such
as organic photovoltaic [25], light emitting devices [26,27],
flexible batteries [28], field effect transistors [29], sensor arrays [30] or radio frequency identification devices [31]. During
the printing operation, the conductive ink, especially designed, is subject to several constraints. Dimensionless studies, based on the rheological properties of the ink and the
printing system parameters, were performed to predict the
ink processability [3235]. Furthermore, three important
phases can be identified in the inkjet printing process: (i)
ejection of the droplet (ii) impact of the droplet onto the substrate (iii) and ink drying. In each phases, the control of some
parameters such as droplet velocity, wettability of substrate,
substrate absorption capacity, and drying speed are crucial in
order to achieve a high print quality. To our knowledge, only
one research team has brought knowledge about the influence of high volume (1100 lL) droplet drying on the CNT
distribution [16]. They found that drying a droplet of CNT
suspension on a wettable surface led to redistribution, accumulation and organization of CNTs along the perimeter of
the droplet.
The purpose of present study was to propose an innovative
method, evaluating the distribution of CNTs within the inkjet
printed films, and also to check the influence of droplet velocity on this CNT distribution. Measurements of electrical properties of the printed films were also performed to relate those
properties to the CNT distribution.

2.

Materials and methods

2.1.

Materials

A commercially available dispersion of PEDOT-PSS from H.C.

Starck (trade name: CLEVIOS P JET) has been used: it consists
in an aqueous dispersion of the conductive polymer PEDOT
doped with poly(styrene sulfonic acid), which plays the role of
counter-ion and assures the suspension electroneutrality [36].
This dark blue solution presents a Newtonian behavior with a
viscosity of 7 mPa s and a surface tension of 29 mN m1 at 25 C.
SWCNT-COOH were purchased from SigmaAldrich and
used as functional element in the conductive ink. This material was produced by electric arc discharge technique. The
average diameter of an individual SWCNT-COOH is
1.4 0.1 nm and the bundles dimensions are approximately
45 nm 0.51 lm.
Two different substrates were printed depending of the
trial nature: Polyethylene terephthalate (PET) sheet and Aluminium foil. The 100 lm thick PET films correspond to the
substrate used for the majority of experiments, while the aluminium foil was used for experiments requiring specific
conditions.

2.2.

CNT ink preparation

SWCNT-COOH were dispersed in aqueous solvent (concentration: 0.5 mg/mL) by sonication during a processing time of
20 min. The sonication process was carried out with a Branson 250 Sonifier (10 mm end cap diameter tip) which output
power was fixed at 35 W. During the treatment, the sample
cup was placed in a bath of ice water in order to prevent rising
of the temperature of the mixture. To monitor the sonication
step a UVvisible technique described by Grossiord et al. has
been applied [37,38]. After the optimum dispersion has been
achieved, the CNT dispersion is centrifuged to remove some
impurities or possible remaining CNT aggregates. Three centrifugation cycles of ten minutes were performed at
3500 rpm and each time, the supernatant was collected. A
small quantity of the initial CNT content is lost during this
step and remains in the residue of centrifugation. The final
suspension obtained was opaque, black and remains stable,
with a surface tension of 71 mN/m and a viscosity of 1 mPa s.
The SWCNT-COOH aqueous suspension was then mixed
with the PEDOT-PSS suspension. In order to optimize the conductivity and the stability of PEDOT-PSS films, a secondary
doping agent (ethylene glycol) was added. In a previous work,
the optimal concentration was found to be 7% in volume [39].
The SWCNT-COOH/PEDOT-PSS ink was obtained by mixing
the finely dispersed CNT suspension and doped PEDOT-PSS
suspension by vigorous stirring. The optimal proportion between the two kinds of conductive suspensions was found
to be 25% in vol. for the CNT suspension and 75% in vol. for
the PEDOT-PSS suspension [11]. The obtained ink has a surface tension of 28 mN/m and a viscosity of 6 mPa s.

2.3.

Inkjet printing of conductive patterns

The CNT conductive ink was printed using a laboratory piezoelectric inkjet printer (Fujifilm Dimatix DMP 2831 with 10 pL

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nominal drop size cartridge) using the following optimized

set of parameters: (i) drop spacing: 15 lm, (ii) substrate temperature: TRoom, (iii) nozzles temperature: TRoom and (v) nozzle
diameter: 21.5 lm. The voltage of ejection which controlled
the drop velocities has been varied. The range of voltage
applicable on Dimatix printer is comprised between 12 and
40 V. In addition, a drop watcher camera coupled with a drop
volume measurement module allows determining characteristics such as drop shape, drop velocity, or drop volume.

2.4.

Microscopy analysis

In order to characterize the CNT networks, microscopy analyses were performed using different techniques at different
scales. Firstly, optical microscopy was carried out to evaluate
the print quality of the deposit. Then, a SEM coupled with an
EDS detector was used for mapping CNT distribution on a
sample surface. To strictly localize the carbon derived from
CNTs, several precautionary measures were taken. Indeed,
no carbon atoms arisen from other materials such as substrate or ink binder must contaminate the sample. To fulfill
this requirement, trials were performed on an aluminum foil
with the aqueous SWCNT-COOH suspension and with the
SWCNT-COOH/PEDOT-PSS ink. For the latest sample, an additional step was executed to degrade and eliminate the PEDOTPSS and the secondary dopant by heating, and therefore the
associated carbon atoms (2 h at 300 C). The EDS spectrums,
shown in Fig. 1, for the aqueous suspension and for the ink
indicate that the same quantity of carbon atoms were identified, which warrants the total elimination of carbons arisen
from the polymer binder.
To perform analyses, a low voltage (3 kV) combined with a
high vacuum (5.6 107 Torr) were applied. To complete the
qualitative analysis, an image processing and analysis program (Image J Area Fraction) was used to perform quantitative analysis. This quantitative study remains an
approximation because the results obtained are influenced
by the microscope setting.
Finally, observation of CNT networks was also performed
using a SEM with a field emission gun (SEMFEG). A low volt-

2605

age of 35 kV was applied to reduce charging effects relative

to the sample in the absence of metalizing. In order to obtain
the best possible resolution, the secondary electron imaging
mode with the In-lens detector was used. To characterize
CNT networks orientation, the Image J plugin Point picker
was used to pick and save a list of segment coordinates corresponding to the CNT positions (300 segments/image).

2.5.

Electrical characterization

The electrical properties were characterized by measuring the

sheet resistance of the printed films with a Jandel Universal
four-probes system, connected to a Jandel RM3 current generator providing a current range from 1 108 to 9.9 102 A. In
this configuration, the two external probes impose a known
current intensity and the two internal probes measure the
corresponding voltage. The expression of the sheet resistance
in this particular configuration is:
Rsquare K 

U
Ohm=square
l

where square represents a surface of 1 mm2; K is a constant

depending on the geometry; U is the measured voltage, in
Volt; I is the set intensity, in Ampere.
To obtain an optimal contact between the four probes and
the CNT printed network, silver plugs corresponding to the
probes were printed with the Dimatix printer on each sample.
Samples are then cured at 90 C during 15 min. Five measurements were taken on each sample and linearity of measurement was checked for positive and negative current
intensities.

3.

Results and discussions

3.1.

CNT Mapping method

Because of their dimensions, CNTs are very difficult to visualize: optical microscopy offers large observation windows but
only investigates very big agglomerates of nanotubes, therefore it doesnt enable to analyse the dispersion at sub-micron

Fig. 1 EDS spectrum comparing the amount of carbon identifying for the SWCNT-COOH aqueous suspensions and for the
SWCNT-COOH/PEDOT-PSS ink after thermal degradation of doped PEDOT-PSS.

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scale [19,40]. Methods such as electron microscopy (SEM,

SEMFEG, TEM) [11,18,19] and atomic force microscopy
(AFM) [20,21] allow the visualization of CNT network on surface and cross section sample views, but the visualization
window remains very small (in the order of lm2). It is therefore difficult to draw conclusion about the whole organization
of the system. In order to solve this problem, the protocol
developed in this work is based on cartographies showing
the carbon elemental distribution in a sample surface by
using an EDS detector. As indicated in experimental part, specific parameters have been selected for EDS in order to obtain
an elemental composition corresponding to the lowest sampling depth (<1 lm) and precautionary measures must be taken to avoid cartography contamination. A simulation of
the interaction depth has been estimated in Fig. 2.
This mapping technique specifically developed in this
work is an innovative way to evaluate CNT dispersion and
has been very useful for analyzing inkjet process parameters
influence. Crucial information about the distribution of CNTs
within the printed patterns was obtained, as shown on Fig. 5.
To our knowledge, it is the first time such analysis is achieved.

3.2.

Dimensionless analysis

Firstly, it was necessary to check that the conductive ink

developed in this work was in accordance with inkjet printing
requirements. In piezoelectric inkjet printing process, the
generation of drops is based on electromechanically induced
pressure wave [22]. The piezoelectric element creates a pressure wave that propagates up to the nozzle exit. In the nozzle

Fig. 2 Simulation of the EDS interaction volume in carbon

material for a low voltage of 3 kV.

region, the pressure wave accelerates the ink and ejects it.
The ink is then broken into a droplet if its kinetic energy is
sufficient to overcome the surface energy interactions. The
process described above is consequently governed by two
phenomena: (i) the propagation of the pressure wave along
the capillary tube and (ii) the conversion of the kinetic energy
of the ink into surface energy [40]. Some recent studies proved
that both phenomena can be characterized by dimensionless
numbers, namely the Weber number (We), the Reynolds number (Re) and the Z number (Z). These dimensionless numbers
allow determining if a droplet is ejected and if it is free of satellite drops [32,41]. In order to generate a droplet, two conditions must be fulfilled. First, the kinetic energy must be higher
than the surface energy of the drop. This is described by the
We number:
2

We

Kinetic Energy qdv

Surface Energy
r

where d is the orifice diameter, v is its velocity, q is the ink

density and r is the surface tension of the liquid. We describe
the kinetic-surface energy conversion governed by both the
speed of the jet and the surface tension. If We is higher than
1, the first condition is fulfilled. The second condition to warrant the drop formation is that the kinetic energy should be
higher than viscous dissipation. This is described by the Reynolds number:
Re

Kinetic Energy
qvd

Dissipated Energy
g

where g is the dynamic viscosity of the ink. Reynolds number

could be used to interpret the viscosity effect of fluids. An approach combining these two dimensionless numbers was
firstly proposed by Fromm [42] in which the fluid properties
are described by the Z number which is equivalent to the inverse of Ohnesorge number (Oh). Oh characterizes the propagation of the pressure wave and its attenuation by viscous
dissipation.
p
qrd
1
Re
p
4
Z
Oh
g
We
As predicted by Fromm [42], the drop formation in a
DOD inkjet printer is only possible for Z > 2. Derby and Reis
[32,43] refined this prediction and found that the processability of an inkjet ink is given for a Z number between 1
and 10, whereas a Z-number larger than ten specifies an
area in which droplet formation is improbable or subject
to satellite drop formation. Finally, Jang et al. [33] redefined
recently the printable range as 4 6 Z 6 14 by considering

Fig. 3 Droplet formation for the SWCNT-COOH/PEDOT-PSS ink with pulse voltage of 30 V.

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Fig. 4 Optimization of SWCNT-COOH/PEDOT-PSS print quality in order to avoid defaults linked to the printer parameters: (a)
too high voltage (b) too high drop spacing (c) too high dry speed (d) optimized parameters.
additional characteristics of printing such as droplet generation and positional accuracy. Printing using a fluid with
Z < 4 will lead to a droplet formation with a long-lived filament, resulting in a degradation of the positional accuracy
and printing resolution. Inks with Z > 14 are also inappropriate for inkjet printing because of their inability to form
a single droplet without the formation of undesired satellites. The suspension and ink characteristics, as well as
the calculated dimensionless numbers, were resumed in
Table 1.
The optimized SWCNT-COOH/PEDOT-PSS conductive ink
fulfills all the conditions to achieve a stable and accurately
printing process with the inkjet printer used in this study.
The SWCNT-COOH aqueous suspension, which is not especially designed for inkjet printing, does not match with all
these requirements. Indeed, its Z number is superior to 14,
which means that a stable printing process will not be
achieved. This suspension is then subject to the forming of
undesired satellite drops or even to the non-ejection and
could not be industrially developed. This suspension was nevertheless printed for producing specific samples (SEM/EDS
analysis) in order to answer some fundamental questions
regarding CNT dispersion within droplet and to emphasize
the impact of doped PEDOT-PSS matrix onto the CNT
organization.
The minimum pulse voltage applicable for conductive ink
studied was 20 V. Below this value droplets could not be
formed and ejected. Fig. 3 displays the droplet formation pro-

cess for the conductive ink with doped PEDOT-PSS at the

pulse voltage of 20 V.
The liquid was ejected from the nozzle and a liquid column was formed. As time progressed the liquid column gradually formed a spherical head like at t = 25 ls. The
characteristic shape of the droplets can then be divided into
two parts: a circular leading part, and a thin ligament extension part. The maximum length of the ligament part is
approximately 300 lm. Between 30 and 35 ls, the liquid column was completely separated from the nozzle. The drop
watcher camera does not allow visualizing the contraction
between the ligament part and the leading part to become a
single droplet. This merging is the most plausible scenario
considering the adequate value of the Z number (Table 1) [32].

3.3.

Printed sample morphological study

3.3.1.

Coffee-ring effect

For conductive tracks, ideal inkjet-printed lines are smooth

and straight. To optimize the electrical performance of the
printed pattern, defaults such as ring-shaped marks, discontinuity of the deposit or edge irregularities have to be avoided
as shown in Fig. 4(ac). With the SWCNT-COOH/PEDOT-PSS
conductive ink, a good optical printing quality was achieved
after an optimization step of the printing parameters
(Fig. 4d) described previously [11]). At this scale, it was not
possible to acquire information about the CNT repartition into
the printed patterns.

Table 1 Calculation of We, Re and Z dimensionless numbers for the SWCNT-COOH suspension and the SWCNT-COOH/
PEDOT-PSS ink from ink and printer properties.
Ink
SWCNT-COOH
suspension
SWCNT-COOH/
PEDOT-PSS ink

r [N m1]

g [Pa s]

q [kg/m3]

Voltage [V]

Nozzle
diameter d [lm]

Volume
V [pL]

Velocity
v [m s1]

We

Re

0.071

0.001

990.1

32

21.5

5.3

24

172

511

38.9

0.028

0.006

985.3

32

21.5

7.4

24

434

85

4.1

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Fig. 5 EDS carbon maps on a line pattern printed with the (a) SWCNT-COOH suspension and with the (b) SWCNT-COOH/
PEDOT-PSS ink. Schematic representation of the process of drop drying after deposition with inkjet printing of an (c) aqueous
colloidal suspension (coffee ring effect) and of a (d) colloidal suspension when Marangoni flows occurs. (Scheme (c and d)
inspired from [38]).

Fig. 5a corresponds to an EDS carbon map of a line pattern

printed with the SWCNT-COOH suspension using an aluminium foil as substrate. The colored dots identify the presence
of carbon and therefore give information about the CNT repartition in the deposited patterns. A higher density of carbon is
recorded at the edges of the pattern in comparison with the
center. This specific distribution may result from the coexistence of two different causes: (i) The first one is the presence
of the coffee ring effect described by Deegan and co-workers [44,45]. In fact, when an aqueous colloidal suspension is
dropped onto a closed and wettable substrate, the suspended
particles tend to move towards the edge of the droplet during
the solvent evaporation, as shown in scheme in Fig. 5c. This
phenomenon occurs because the water evaporation rate is
the highest at the edge of the suspension droplet, which
causes a flow toward the pattern edges. The phenomenon is
met on the line pattern because the merge of several closed
droplets leads to a redistribution of fluids and particles within
the global pattern. In this case, the colloidal particles migrate
towards the line edges. In this phenomenon, the viscosity of
the fluid is a crucial parameter which influences the suspended particle migration. (ii) The second cause is that, in
inkjet process, the ink droplets land on the substrate with
an outward velocity. During the droplet impaction, the
spreading is mainly driven by the inertia of the drop and is
slowed by viscous effect. This outward velocity may lead to
the transport of some particles on the outside rim and may
accentuate the coffee ring effect.

The same study was also performed with the optimized

SWCNT-COOH/PEDOT-PSS ink after the elimination by heating of carbon atoms arisen from the doped conductive polymer binder. Results are shown in Fig. 5b. By using an
aluminium foil as substrate, the print qualities with the ink
was degraded because of poor affinity between the ink and
the substrate, and certainly because of the thermal treatment
applied to eliminate PEDOT-PSS and co-solvent (see experimental part). The coffee ring effect still exists but it is hugely
attenuated. Indeed, the yellow dot distribution is more homogeneous than for the aqueous SWCNT-COOH suspension.
This comparison between the two colloidal suspension
behaviors emphasizes that the doped PEDOT-PSS suspension
influences the CNT arrangement during drying and limits the
coffee ring effect, resulting in a more homogeneous distribution of the CNTs. The explanation of this more homogeneous
distribution certainly derived from the combination of several
causes: (i) the first one was recently described by Lim et al.
[46]. They demonstrated that the addition of a high temperature boiling and low surface tension component as minor solvent in the ink induces a recirculation flow called Marangoni
flow [47] in the droplets as shown in Fig. 5d. The secondary
dopant (ethylene glycol 7% in vol.) introduced into the
SWCNT-COOH/PEDOT-PSS ink fulfills all the conditions to induce a Marangoni flow during the drying step and could explain this better homogeneity of CNT dispersion. (ii) A
second explanation for the absence of coffee-ring effect
may also relate to the fact that there is polymer chain in

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Table 2 Quantification by ImageJ of EDS carbon maps

colored dots at different location of the printed patterns, for
the SWCNT-COOH suspension and for the SWCNT-COOH/
PEDOT-PSS ink. The calculation of ratios between different
locations are also presented.
SWCNT-COOH SWCNT-COOH/
suspension
PEDOT-PSS ink
Pattern location Edges
[%]
Center
Ratio [%/%]
[edges/center]

51.9
8.1
6.4

42.0
28.9
1.4

the way which can impede the complete migration of the

CNTs to the periphery. (iii) Finally, the viscosity of the fluid

2609

can also influence the particles migration. Indeed, during

the impaction process, the ink spreading, mainly tailored by
the drop inertia, can be attenuated by viscous effect. Furthermore, during the drying process, a higher viscosity which
means a higher resistance to flow may also lead to a slowdown of the particle migration, resulting in a more homogeneous distribution. In our case, the viscosity is six times
higher for the SWCNT-COOH/PEDOT-PSS ink than for the
SWCNT-COOH suspension.These three phenomena may
coexist but it appears very difficult to determine which one
is the more influencing considering CNT distribution.
To quantify the coffee ring effect, the image processing
and analysis program Image J was used. This program allows
calculating the percentage of colored dots in a given area of
the printed pattern. Results for different location in the

Fig. 6 SEMFEG observations of (a) a SWCNT-COOH suspension printed line pattern at different location (center (b) and edges
(c and d) of the patterns) together with calculation of CNT orientation according to xy orientation presented in (a).

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printed layers were given in Table 2 for the SWCNT-COOH

suspension and for the SWCNT-COOH/PEDOT-PSS ink.
The calculated ratio between the percentages obtained at
the edges and at the center of the printed patterns corroborates the EDS carbon maps (Fig. 5(a and b)). Indeed, there
are about 6 times more SWCNT at the edge than at the center
for the SWCNT-COOH suspension. The value of this ratio
(edge/center) is significantly higher for this suspension than
for the SWCNT-COOH/PEDOT-PSS ink. The presence of the
doped PEDOT-PSS suspension completely changes the CNT
distribution.

3.3.2.

Organization of the CNT network

As the distribution has been determined, it was important to

try to evaluate if any orientation was present. Therefore,
observations of the CNT networks were performed at a
nano-scale. Fig. 6 illustrates the CNT network formed at different locations within a SWCNT-COOH aqueous suspension
printed line. Analyses of CNT orientation are detailed next
to each corresponding image. On Fig. 6a, the xy orientation selected is presented on one example of pattern. Fig. 6b corresponds to the center, whereas Fig. 6(c and d) correspond to
the near periphery and the periphery of the printed pattern,
respectively.
It confirms that the density of SWCNT-COOH seems to be
higher at the edges than in the center of the printed patterns.
This observation corroborates the coffee-ring effect observed
on the carbon maps (Fig. 5a). In addition, different behaviors
were identified. In the center of the printed pattern, the
SWCNT-COOH network appears to be randomly formed,
whereas at the edges of the sample an ordered structure with
orientated CNTs is observed. The formation of packed
SWCNT-COOH bundles can be caused by the rapid evapora-

tion at the printed pattern edges, promoting high-level ordering. The orientation seems to vary with the location in the
printed patterns: at the periphery, the orientation of CNTs appears to be parallel to the edges (mean angle around 10),
whereas in the close periphery, the CNT orientation appears
to be near perpendicular to the edges (mean angle around
85). A scheme of such orientation is proposed in Fig. 7a.
The reason of this orientation may certainly result from
the flow induced by the coffee ring effect. Indeed, when the
CNTs are carried towards the edges of the printed pattern,
their orientation follows the flow direction and when they
are moving close to the edge, they piled up and changed their
direction according to the geometrical constraint. Another
plausible explanation to this self-organization was found in
literature [48] and depends from the synthesis method of
the CNTs employed. The SWCNT-COOH used for this work
were generated through the electric arc discharge method in
which CNTs are formed in the presence of catalyst metal particles such as Fe, Co or Ni. These metal particles considered as
impurities can be entrapped inside CNTs. CNTs which have
metallic nanoparticles entrapped can be aligned and stick together by mutual magnetic attraction. Therefore, this phenomenon can also be at the origin of the SWCNT-COOH
alignment at the edge of the printed patterns or can amplify
it. The non-magnetic CNTs remain mobile and randomly arranged. The detection of such metallic nanoparticles in the
printed patterns was supported by an EDS analysis (Fig. 7b)
proving the presence of nickel more abundant at the edge
than in the center of the printed patterns.
Fig. 8 corresponds to a SEMFEG observation of SWCNTCOOH/PEDOT-PSS conductive ink. The doped PEDOT-PSS suspension complicates the observation of the CNT network because it acts as a mask. To visualize the network, the

Fig. 7 (a) Schematic illustration of the different orientation depending on the pattern location (b) EDS analysis proving the
presence of nickel in more abundance at the edge than in the center of the printed patterns.

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2611

Fig. 8 (a) SEM-FEG observations of the CNT network within the SWCNT-COOH/PEDOT-PSS conductive ink by electronic
scanning degradation (b) Schematic illustration a network above the percolation threshold: presence of conducting pathway.

conductive polymer suspension was degraded progressively

by several electronic scans.
Whatever the location, a random network, above the
SWCNT-COOH percolation threshold, was obtained and confirmed by picking technique. A graph (not presented here)
similar to Fig. 6b was obtained. This observation warrants
the presence of conducting pathways as illustrated in the
scheme of Fig. 8 and highlights the important influence of
doped PEDOT-PSS suspension on the CNT orientation.

3.4.

Droplet ejection: influence of drop velocity

In addition to ink formulation it was also important to check

if some process parameters could also influence distribution
and orientation. During the droplet ejection phase, the influence of droplet velocity onto CNT arrangement and electrical
properties was explored. The velocity of droplet is driven by
the pulse voltage which has also an impact on the droplet volume. Indeed, the influence of the pulse voltage on the droplet
volume and on the speed was presented in Fig. 9.
It shows that the minimum droplet volume at 22 V was
about 5 pL, with the average velocity of 12 m s1. Up to a pulse
voltage of 40 V, the droplet volume increases slightly to 10 pL
with a velocity of 26 m s1. These values of drop velocity appear high for the field of DOD ink-jet but are in accordance
with the Dimatix printer DMP-2800 specification. The velocity
increases linearly under the voltage range 2232 V. Then, a
break of linearity is observed at 34 V and a linearity trend is
recovered up to 40 V. The droplet volume also increased
slightly under the entire range of voltage but have also a pla-

teau range which allows having different speeds for similar

volume. Therefore, to focus exclusively on the velocity impact, the shortened velocity range 1824 m s1 is more adequate. It corresponds to a quite stable volume, equivalent to
7.5 pL. Fig. 10 compares the CNT distribution within a
printed line for the suspension and the ink.
For the SWCNT-COOH suspension (Fig. 10a), the velocity
increase leads to less definition of the line pattern with presence of irregularities. Regarding the CNT arrangement, the
coffee ring effect seems to be slightly accentuated by the
speed. The data obtained from the image analysis method
confirmed this trend (Cf. Table 3). The calculated ratio between the percentages obtained at the edges and at the center
of the printed patterns is quite superior for the highest than
for the lowest speed.
For the SWCNT-COOH/PEDOT-PSS conductive ink, no obvious influence of the drop velocity was recorded. This observation was also validated by the image analysis data in Table 3.
The effect of drop velocity appears attenuated for the
SWCNT-COOH/PEDOT-PSS ink certainly because of the combined effects of viscosity, Marangoni flow and polymer chains
as already explained in Section 3.3.1.
Considering the high cadence of industrial printing, this
result is encouraging. Table 4 resumes the values of sheet
resistance obtained for the printing of five superimposed layers for different levels of drop velocity in the case of the optimized SWCNT-COOH/PEDOT-PSS ink.
The sheet resistance values emphasize that the increase of
velocity has no obvious influence on sheet resistance. However, this value confirms higher conductivity in comparison

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4 9 ( 2 0 1 1 ) 2 6 0 3 2 6 1 4

Table 4 Sheet resistance measurements onto solid areas

printing patterns for the superimposition of five layers of
SWCNT-COOH/PEDOOT-PSS ink at different level of velocity.
Drop velocity (m s1)
Drop volume (pL)
Rsheet (ohm/sq)

Fig. 9 Relation of droplet velocity and volume versus pulse

voltage for SWCNT-COOH/PEDOT-PSS conductive ink.

with the SWCNT-COOH suspension (>4 kX/sq), which can be

attributed to the conductivity of such polymers and/or to
the CNT organization.

4.

Conclusion

In this work, the distribution and orientation of CNTs within

inkjet printed films was investigated for a SWCNT-COOH
aqueous suspension and for a SWCNT-COOH/PEDOT-PSS
ink. In a first step, a preliminary study based on dimensionless numbers was performed in order to predict the jettability
of the two CNT suspensions. Then, the droplet formation and
the printed sample morphology were evaluated. All the results obtained demonstrate the better jettability of the
SWCNT-COOH/PEDOT-PSS ink.
The core investigation was performed using an innovative
method allowing the localization of CNTs within the ink film
at a relatively large scale. Thanks to this method and SEM
FEG observations, crucial information were obtained about
the CNT distribution and organization within the printed

18
7.5
401(+/59)

24
7.4
462(+/15)

ink film. Drying by evaporation of a SWCNT-COOH suspension droplet leads to an accumulation and organization of
the CNTs along the perimeter of the printing patterns. This
drawback could be also considered as an advantage if orientated CNTs are expected. This phenomenon is clearly attenuated with the SWCNT-COOH/PEDOT-PSS ink. The CNT
network within this conductive ink is less impacted by the
coffee-ring effect and therefore is homogeneous and continuous whatever the location within the printed pattern. It confirms that the positive impact on conductivity caused by the
addition of doped PEDOT-PSS suspension is linked to the
addition of conductive polymers but also to the induced distribution and orientation of CNTs. On the contrary, it was also
found that an increase in droplets ejection velocity have an
impact on the printing of the SWCNT-COOH suspension,
resulting in a slight accentuation of the coffee-ring effect.
However, this was not observed with the SWCNT-COOH/PEDOT-PSS ink.
Finally, this work opens a new road to examine the influence of inkjet formulation and printing process on carbon
nanotubes distribution, which is essential for understanding
and improving the electrical properties of the printed patterns. Further work will be dedicated to investigate influence
of some other parameters on CNT organization such as wettability of substrate, absorption capacity of the substrate and
drying speed, which are crucial parameter to achieve high
print quality.

Fig. 10 EDS carbon map for the printing of one layer line pattern onto aluminium foil for (a) the SWCNT-COOH suspension
and (b) the SWCNT-COOH/PEDOT-PSS ink at different ejection speed.

Table 3 Quantification by Image J of EDS carbon maps colored dots at different location of the printed patterns and at
different speed of ejection, for the SWCNT-COOH suspension and for the SWCNT-COOH/PEDOT-PSS ink.
SWCNT-COOH suspension
1

Pattern location [%]

Ratio [%/%] [edges/center]

Edges
Center

SWCNT-COOH/PEDOT-PSS ink
1

18 m s

24 m s

53.4
8.2
6.5

58.3
7.9
7.4

18 m s1
42.1
28.5
1.5

24 m s1
35.2
20.6
1.7

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4 9 ( 20 1 1 ) 2 6 0 326 1 4

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