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Microwave Flash Sintering of Inkjet-Printed Silver
Tracks on Polymer Substrates
By Jolke Perelaer, Mark Klokkenburg, Chris E. Hendriks, and
Ulrich S. Schubert*
Within the last few decades inkjet printing has grown into a
mature noncontact patterning method, since it can produce
large-area patterns with high resolution at relatively high speeds
while using only small amounts of functional materials.[1–3] The
main fields of interest where inkjet printing can be applied
include the manufacturing of radiofrequency identification
(RFID) tags,[4–6] organic thin-film transistors (OTFTs),[7–9] and
electrochromic devices (ECDs),[10,11] and are focused on the
future of plastic electronics.[12]
In view of these applications on polymer foils, micrometer-
sized conductive features on flexible substrates are essential. To
fabricate conductive features onto polymer substrates, solution-
processable materials are often used. The most frequently used
are dispersions of silver nanoparticles in an organic solvent.[13–15]
Inks of silver nanoparticle dispersions are relatively easy to
prepare and, moreover, silver has the lowest resistivity of all
metals (1.59 mV
cm). After printing and evaporation of the
solvent, the particles require a thermal-processing step to render
the features conductive by removing the organic binder that is
present around the nanoparticles. In nonpolar solvents, long alkyl
chains with a polar head, like thiols or carboxylic acids, are usually
used to stabilize the nanoparticles.[16,17] Steric stabilization of
these particles in nonpolar solvents substantially screens van der
Waals attractions and introduces steep steric repulsion between
the particles at contact, which avoids agglomeration.[18] In
addition, organic binders are often added to the ink to assure not
only mechanical integrity and adhesion to the substrate, but also
to promote the printability of the ink.[16]
Nanoparticles with a diameter below 50 nm have a significantly
reduced sintering temperature, typically between 160 and 300 8C,
which is well below the melting temperature of the bulk material
(Tm ¼ 963 8C).[19,20] Despite these low sintering temperatures
conventional heating methods are still not compatible with
common polymer foils, such as polycarbonate (PC) and
[*] Prof. U. S. Schubert, Dr. J. Perelaer, C. E. Hendriks
Laboratory of Macromolecular Chemistry and Nanoscience
Eindhoven University of Technology and Dutch Polymer Institute (DPI)
PO Box 513, 5600 MB Eindhoven (The Netherlands)
E-mail: u.s.schubert@tue.nl
Dr. M. Klokkenburg
Holst Centre, High Tech Campus 31, 5656 AE Eindhoven
The Netherlands
Prof. U. S. Schubert
Laboratory of Organic and Macromolecular Chemistry
Friedrich-Schiller-University Jena
Humboldtstr. 10, 07743 Jena (Germany)
DOI: 10.1002/adma.200901081
Adv. Mater. 2009, 21, 1–5 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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polyethylene terephthalate (PET), due to their low glass-transition
temperatures (Tg). In fact, only the expensive high-performance
polymers, like polytetrafluoroethylene (PTFE), poly(ether ether
ketone) (PEEK), and polyimide (PI) can be used at these
temperatures. This represents, however, a significant drawback
for the implementation in a large-area production of plastic
electronics, being unfavorable in terms of costs. Furthermore, the
long sintering time of 60 min or more that is generally required to
create conductive features also obstructs industrial implementa-
tion. Therefore, other techniques have to be used in order to
facilitate fast and selective heating of materials.
One selective technique for nanoparticle sintering that has
been described in literature is based on an argon-ion laser beam
that follows the as-printed feature and selectively sinters the
central region. Features with a line width smaller than 10 mm
have been created with this technique.[21] However, the large
overall thermal energy impact together with the low writing speed
of 0.2 mm s1 of the translational stage are limiting factors.[22]
A faster alternative to selectively heat silver nanoparticles is to
use microwave radiation.[23] Ceramics and other dielectric
materials can be heated by microwaves due to dielectric losses
that are caused by dipole polarization. Under ambient conditions,
however, metals behave as reflectors for microwave radiation,
because of their small skin depth, which is defined as the distance
at which the incident power is reduced to half of its initial
value.[24] The small skin depth results from the high conductance
s and the high dielectric loss factor e00 together with a small
capacitance. When instead of bulk material, the metal consists of
particles and/or is heated to at least 400 8C, the materials absorbs
microwave radiation to a greater extent.[25,26] It is believed that the
conductive particle interaction with microwave radiation, i.e.,
inductive coupling, is mainly based on Maxwell–Wagner
polarization, which results from the accumulation of charge at
the materials interfaces, electric conduction, and eddy cur-
rents.[25] However, the main reasons for successful heating of
metallic particles through microwave radiation are not yet fully
understood.
In contrast to the relatively strong microwave absorption by the
conductive particles, the polarization of dipoles in thermoplastic
polymers below the Tg is limited, which makes the polymer foil’s
skin depth almost infinite, hence transparent, to microwave
radiation. Therefore, only the conductive particles absorb the
microwaves and can be sintered selectively. Recently, it has been
shown that it is possible to create conductive printed features with
microwave radiation within 3–4 min.[23] The resulting conductiv-
ity, however, is only approximately 5% of the bulk silver value.
In this contribution, we present a study on antenna-supported
microwave sintering of conducted features on polymer foils. We
1

inkjet printed antenna structures using a colloidal dispersion of
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silver nanoparticles onto a flexible polyethylene naphthalate
(PEN) foil (see Fig. 1a for the template). The template consists of
four metal areas, each having a surface area of 11 mm2.
Figure 1. Schematic representation of the printed template (a) with four
silver electrodes/antennae in gray and a single silver line inkjet printed on
top of the antennae in black. The total length of the line is 1.6 cm. Influence
of the total surface of the four electrodes on the template for an initial line
resistance of 100 V (b) and 1 kV (c) on microwave flash exposure for 1–60 s.
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Subsequently, curing of the antenna structures was performed at
110 8C for 60 min. These antennae were used both to measure the
resistance of the single ink line and to capture electromagnetic
waves. After this, a single silver ink line was printed over the
metallic probes (black line in Fig. 1a) and quickly cured in an oven
for 1–5 min at a temperature of 110 8C. This relatively short time
was chosen to stimulate solvent evaporation, but to minimize
thermal curing. After this treatment, the single line had a
relatively high resistance in the order of 102 to 104 V. The sample
was subsequently exposed to microwave radiation for at least 1 s,
while applying the lowest set-power of 1 W. This resulted in a
pronounced decrease of the resistance of which the exact outcome
depends on the initial resistance.
The antenna effect, which reflects the capability to absorb
microwaves into the material, was studied systematically by
altering the surface area of the electrodes of the template. When
increasing the size of the electrodes a rapid decrease of the
resistance after microwave exposure was revealed, as is shown in
Figure 1b and c for pre-dried samples. This may be explained by
the improved absorption of the microwaves due to an increased
surface area of the electrodes.
The antenna effect, however, is larger when the initial line
resistance is small (Fig. 1b), which is likely due to enhanced heat
conduction from the electrodes to the ink line. For ink lines with
an initially large resistance (Fig. 1c), the energy transfer is still
very effective, although the total antenna area has less impact on
the final resistance. The data obtained in the absence of antennas
(A ¼ 0 mm2) clearly demonstrate that the energy absorption by
the printed line is negligibly small. The absorption of microwave
radiation may be improved by the presence of antennae due to a
subsequently smaller impedance mismatch between air and
sample. According to Zuckerman et al. the intrinsic impedance
Z of a circuit relative to free space is given by
pffiffiffiffiffi
Z ¼ Z0 " (1)
where Z0 is the impedance of the free space (Z0 ¼ 377 V) and e* is
the complex permittivity of the circuit relative to free space. The
complex permittivity is related to the dielectric constant and loss
factor according to
s
"r ¼ "0 þ i"00 ¼ "0 þ i (2)
v
"0
where the real part e0 is the ability of the material to store energy
and where the imaginary part e00 accounts for the losses via energy
dissipation. The reflection, i.e., impedance mismatch Z/Z0, scales
with the square root of the complex permittivity e* and thus, in
our experiments, with the resistance of the electrodes, which
depends on their total surface area.[27]
Figure 2 depicts the effect of the initial resistance of the printed
line on the final resistance after microwave exposure for different
times. When the flashing time is equal to 1 s, the resistance can be
decreased to a few Ohms per line, only if the initial resistance is
within a range of 102 to 104 V. Above a threshold if 105 V, the
microwave coupling and transfer at the antenna-line interface is
insufficient to accomplish pronounced sintering of the nano-
particles and to form a percolating network through the line.
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Figure 2. Effect of the initial line resistance (Rbefore) on the resistance after Figure 3. Effect of the line width on the resistance per line after 1–60 s
microwave flash exposure (Rafter) for 1 or 60 s. microwave flash exposure.

Therefore, longer sintering times are necessary for lowering the close-up of the unsintered but pre-cured track is depicted, where
resistance. As shown in Figure 2, an exposure of 60 s increases the silver nanoparticles with a typical diameter of 30–50 nm can
the initial threshold resistance from 105 V up to 107 V. Moreover, still be distinguished individually. Upon drying, the particles
higher power settings and/or longer exposure times would even probably have lost a part of their organic protecting shell, which
further increase this threshold value. causes the particles to form a percolating pathway for the
To highlight the effect of the surface area of the ink line on the electrons in an early stage.[16] After microwave flash exposure
final resistance, lines were inkjet printed onto the foil with most of the organic material has been removed and the particles
modified surface wetting properties, while using equal print
settings to dispense the same volume of material. On the one
hand, the surface wetting was decreased by increasing the platen
temperature to 60 8C, which stimulates solvent evaporation and
therefore results in a different line geometry.[3,28] On the other
hand, a plasma surface treatment was applied to increase the
surface energy, which improves the wetting behavior of the ink,
and consequently gives broader lines. The line width was
measured to be 172 and 161 mm for lines printed at room
temperature and 60 8C, respectively, while after plasma treatment
the lines were 353 mm in width. Figure 3 shows the effect of the
line width on the resistance after microwave flash exposure. It can
be inferred that a narrow line shows a three times higher
resistance than a broad line for sintering times shorter than 10 s.
This suggests that there is a positive correlation between surface
area of the line, which is directly linked to the line width, and the
amount of energy absorbed. However, this surface effect
diminishes after 30 s of microwave exposure. This indicates that
the surface area of the electrodes mainly determines the effective
sintering time.
The electrical resistivity r of an inkjet printed line was then
calculated from the resistance R, the length ‘, and the cross
sectional area A of the line, using r ¼ R
A=‘. The maximum
conductivity ð1=rÞ for the maximum surface area (44 mm2) of the
antennae was found to be 34% when compared to the theoretical
value of bulk silver. The lowest revealed conductivity was 10% for
the antennae with a surface area of 20 mm2. This value, however,
is significantly larger than the 5% that was reported previously for Figure 4. Scanning electron microscopy (SEM) images of an inkjet printed
silver track on a polymer substrate before (a) and after sintering (b). The
microwave sintering.[23] unsintered track (a) shows a detailed view of the silver nanoparticles with a
Scanning electron microscopy (SEM) images of the printed typical diameter between 30 and 50 nm. A sintered track (b) after flash
silver tracks in Figure 4 show the morphology and particle exposure to microwaves with a total electrode area of 20 mm2. The inset
packing within the line before and after sintering. In Figure 4a, a shows a more detailed view into the track.

Adv. Mater. 2009, 21, 1–5 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 3
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have merged, i.e., sintered, into larger agglomerates – as shown
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by the cross-section in Figure 4b. In Figure 4b, the bottom part is
the polymer foil and the top layer is the as-printed silver line,
which is depicted in more detail in the inset. It can also be seen
that the agglomerates form a relatively dense packed layer of
silver, which increases the amount of percolating pathways for the
electrons through the line. This also explains the relatively high
conductance values of 34%.
Since it is mainly the antenna that directs the electromagnetic
microwaves to the target structure, sintering should also take
place when the antennae are in the vicinity of the target structure,
instead of in direct contact. Therefore, additional experiments
were performed where a single line was inkjet printed between
the antennae without making contact to the antenna structures.
After exposure to microwave radiation for one second the line
showed pronounced sintering, but the conductance was found to
be lower than when a direct contact mode was used. Again, the
total surface of the antennae determines the amount of sintering
that takes place, where larger antennae structures lead to an
enhanced effect.
In conclusion, we have shown that flash microwave sintering
of inkjet printed colloidal dispersions on thin polymer substrates
strongly depends on the total antenna area, the pre-curing time,
and the geometry of the line. The presence of conductive
antennae unambiguously promotes nanoparticle sintering in
pre-cured ink lines, to an extent that depends on the total area of
the antennae. This antenna effect is more pronounced if the ink
line already exhibits conductivity. We believe this is due to the
decreased mismatch between the impedance of air and sample.
Using metal antennae, we have found that 1 s is sufficient to
obtain pronounced sintering by microwave heating. The degree
of sintering for these short exposure periods, however, strongly
depends on the initial resistance of the pre-cured ink lines.
Furthermore, increasing the width of the lines enhances the
initial conductivity raise due to improved energy absorption as a
result of the increased surface area.
After microwave flash sintering, the tracks revealed con-
ductivity values of 10 to 34% when compared to the theoretical
value of bulk silver, which is significantly higher compared to
conventional heating methods. The procedure of printing and
subsequently microwave flash sintering can be used in
production of conductive features with low materials usage on
common polymer substrates in printed electronics, such as large
area fabrication of RFID tags or solar cells. Its major advantage
pertains to both the high process speed and the low processing
temperature, which reduce processing costs, as common polymer
foils like PEN can be used.
Experimental
A silver nanoparticle dispersion in an ethylene glycol/ethanol mixture was
purchased from Cabot (Cabot Printing Electronics and Displays, USA). The
silver ink contains 20 wt% of silver nanoparticles, with the particle
diameter ranging from 30–50 nm. The viscosity and surface tension of the
ink were 14.4 mPa
s and 31 mN m1, respectively. Transparent, colorless
polyethylene naphthalate (PEN, DuPont Teijin, The Netherlands, 125 mm
thickness) film with a glass transition temperature of 120 8C was used as
substrate material. Prior to printing, the foils were cleaned with ethanol. A
template for four-probe resistance measurements was printed onto
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the foil, as displayed in Figure 1a, and heated in an oven for 60 min at
110 8C.
Plasma treatment was performed using a Branson IPC S2100/11220
apparatus with a 2000 TI controller, operating at a frequency of 13.56 MHz.
The power and time were set to 600 W and 1 min, respectively, and nitrogen
was used as carrier gas (500 mL min1).
Inkjet printing was performed using a piezoelectric Dimatix DMP 2800
system (Dimatix-Fujifilm Inc., USA), equipped with a 10 pL cartridge
(DMC-11610). The print head contains 16 parallel squared nozzles with a
diameter of 30 mm. The dispersion was printed at a voltage of 28 V, using a
frequency of 20 kHz and a customized waveform. The printing height was
set to 0.5 mm, while using a dot spacing of 20 mm.
The as-printed structures were sintered in capped reaction vials using
the Biotage Initiator monomodal microwave system, operating at
frequency of 2.45 GHz, which corresponds to a wavelength of 12.2 cm.
The used monomodal microwave did not show an influence on the vertical
rotation of the sample. However, there is a dependency of the vertical
placement within the microwave chamber to the absorption of the
microwaves. Therefore, all samples were placed exactly in the center of
microwave chamber. The power was set to its minimum of 1 W. Surface
topography, thickness and cross-sectional areas of the printed silver tracks
were measured with an optical profilometer (Fogale Zoomsurf, France).
Scanning electron microscopy (SEM) images were taken using a FEG
E-SEM XL30 (Philips, The Netherlands).
Acknowledgements
The authors would like to thank the Dutch Polymer Institute for financial
support. The research of Jolke Perelaer forms part of the research program
(#546) of the Dutch Polymer Institute (DPI).
Received: March 31, 2009
Revised: June 2, 2009
Published online:
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