Electrical sintering characteristics of inkjet-printed conductive Ag lines on a

paper substrate
Shin Jang, Dong Jun Lee, Dohyung Lee, Je Hoon Oh
Department of Mechanical Engineering, Hanyang University, 1271 Sa3-dong, Sangrok-gu, Ansan, Gyeonggi-do 426-791, Republic of Korea
a b s t r a c t a r t i c l e i n f o
Available online 16 May 2013
Keywords:
Electrical Sintering
Inkjet printing
Ag nanoparticle ink
Paper substrate
Resistivity
Initial resistance
Grain growth
The electrical sintering characteristics of inkjet-printed line patterns on a paper substrate were investigated by
varying initial pattern resistance, input voltage, sintering time, and input voltage prole. The initial resistance
was controlled by preheating the patterns, and its range was between 500 and 5 M. Depending on the
input voltage and initial resistance, there exist three different regions: sintering, no change, and blowout.
While no sintering is observed for too high initial resistance, blowout of printed lines occurs for a larger input
voltage. For the initial resistance lower than ~100 k and the input voltage ranging from 20 V to 40 V, all the
printed lines are electrically sintered within a short time without damaging the underlying paper substrates.
When using the two-step voltage prole, the nal resistance of lines becomes ve times smaller than the resis-
tance with the one-step voltage prole due to the increase in the grain size and the reduction in the void area,
and no burning or blowout occurs in the lines. Due to its many advantages, the electrical sintering can provide
a fast, reliable and effective way to fabricate high quality inkjet-printed conductive patterns for various printed
electronics applications.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Over the past few decades, printed electronics has become a prom-
ising technique to overcome the drawbacks of conventional lithography
for various elds such as thin lm transistors [1,2], solar-cells [3], and
biosensors [4]. Particularly, inkjet printing technology can be used to di-
rectly print dielectric layers, electrodes, and electric circuits without any
further processing, resulting in low production cost and a simple and
waste-free process [58].
Metal nanoparticle ink is widely used in inkjet printing to form con-
ductive patterns including electrodes and electrical circuits. Metal
nanoparticles are suspended in the solution with an organic binder and
dispersing agent. These act as suspending agents to encapsulate metal
nanoparticles to prevent agglomeration between the nanoparticles. A
post-thermal sintering process is therefore required to form the electri-
cally conductive path by removing the agents that prevent conductivity
after printing the ink onto the substrate. Due to the high surface-to-
volume ratio of nanoparticles, the sintering temperature is much lower
than that of bulk materials. While the melting point of bulk silver is
about 961 C, the sintering temperature of nanoparticle silver ink is in
the range of 150 C to 250 C, depending on the concentration and
type of suspending agents and the nanoparticle size. Although the
sintering temperature is low, traditional thermal sintering process can
cause thermal degradationof underlyingsoft substrates suchas thermal-
ly sensitive polymers and papers. Another drawback of the thermal
sintering is a long processing time. Therefore, an alternative sintering
process that can provide desired electrical characteristics in a fast and ef-
cient way is essential for high-throughput production.
To overcome these obstacles, several methods suchas light sintering
[9], microwave sintering [10,11], plasma sintering [12], laser sintering
[13] and coalescence of nanoparticles without heating [14] have been
investigated. These methods are still in the development stage and are
not proved to be practical for the fast and reliable sintering yet. In this
work, we introduced an electrical sintering method combined with a
preheating process. For electrical sintering, when the voltage is applied
to the printed pattern, the joule heat is generated along the pattern
within a very short time. This method is fast and highly selective, and
it does not damage underlying substrates. It is also more effective
than thermal sintering since only the conductive patterns are heated
rather than the entire substrate.
The effects of initial patternresistance, applied input voltage and time,
and input voltage prole on the sintering characteristics of Ag lines
inkjet-printed on a photo paper were investigated after a preheating pro-
cess. The initial resistance was varied by controlling the preheating tem-
perature and time. The sintering performances were characterized with a
eld emission scanning electron microscope (FE-SEM), an optical micro-
scope, and an oscilloscope. Various conditions related to stable electrical
sintering without defects were discussed in this study.
2. Experimental details
Commercial photo paper (HC-4020G, Hansol Co.) with a 230 m
thickness, which can endure up to 120 C, was used as a substrate.
Thin Solid Films 546 (2013) 157161
Corresponding author. Tel.: +82 31 400 5252; fax: +82 31 400 4705.
E-mail address: jehoon@hanyang.ac.kr (J.H. Oh).
0040-6090/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2013.05.015
Contents lists available at ScienceDirect
Thin Solid Films
j our nal homepage: www. el sevi er . com/ l ocat e/ t sf
Ag nanoparticle ink (NPS-J, Harima Chemical Co., Japan), which con-
tains 63.7 wt.% Ag nanoparticles in tetradecane with average particle
sizes of around 10 nm, was printed onto the photo paper to form line
patterns using a single piezoelectric printhead with a 30 m nozzle
diameter (MicroFab Co.). The printed line dimensions were 5 mm,
90 m and 1 m in length, width and thickness, respectively. The
thermal sintering condition recommended by the manufacturer is
220 C for 1 h.
Since the printed line's resistance just after printing was too high to
be electrically sintered, the printed patterns were preheated on a hot
plate at 100 C for 5 to 10 min to provide the initial resistance. The
initial resistance was varied from 500 to 5 M depending on the
preheating time. A DC power analyzer (N6705B, Agilent Co.) and a
probe station were usedto apply voltage on the patterns. After electrical
sintering, resistance was measured using an LCR meter (LCR-8101,
GWINSTEK Co.). The pattern shape and its microstructure were
captured by an optical microscope (BX51M, Olympus) and an FE-SEM
(JSM-6700F, JEOL).
Fig. 1 illustrates the schematic of the electrical sintering system
consisting of the DC power analyzer, the probe station with a tip diam-
eter of 1 m, and an auxiliary resistor (R
s
) of 300 connected in series.
The DC power analyzer can generate various voltage waveforms such
as constant, sinusoid and pulse. Once voltage is applied, the joule heat
is created within the printed pattern, thereby removing the organic
binder and dispersing agent and melting the nanoparticles. During the
sintering process, R
s
inuences the nal resistance of the pattern and
plays a role in protecting the pattern from burning by abrupt reduction
of resistance.
3. Results and discussion
Fig. 2 shows FE-SEM images of the printed line pattern before and
after preheating at 100 C. No damage is observed on the photo paper
used in this work at this preheating temperature. As shown in Fig. 2(a),
the residual liquid is still left in the pattern before preheating even
though the pattern was sufciently dried after printing. After preheating
for 5 min, there is no residual liquid in the pattern, but graingrowthdoes
not occur either, as seen in Fig. 2(b), since the preheating temperature is
much less than the recommended thermal sintering temperature. At a
xed preheating temperature, the preheating time determines the initial
resistance of the printed line. When the preheating time is 5 min, the ini-
tial resistance is 5 M. As the time increases to 10 min, the resistance de-
creases to 500 due to the grain growth with the preheating time in
Fig. 2(c).
The inuences of initial resistance, applied voltage, and sintering
time on the nal line resistance are presented in Fig. 3. With a xed
sintering time of 5 s, the nal line resistance decreases with increas-
ing the applied voltage for all the initial resistances (Fig. 3(a)). At a
lower input voltage of 15 V, the nal resistance is dependent on the
initial resistance. In contrast, the lines have the same nal resistance
at a higher input voltage regardless of the initial resistance. If the
input voltage is not sufcient to generate the joule heat in the line,
sintering process is not able to begin. With a xed input voltage of
25 V, the nal resistance is not affected by the sintering time except Fig. 1. Schematics of the electrical sintering system used in this work.
Fig. 2. FE-SEM images of the printed line pattern (a) before preheating, (b) after pre-
heating at 100 C for 5 min, and (c) after preheating at 100 C for 10 min.
158 S. Jang et al. / Thin Solid Films 546 (2013) 157161
for a higher initial resistance (Fig. 3(b)). This is because there is an
abrupt drop followed by a leveling off in the line resistance just
after applying the input voltage as long as the input voltage is suf-
cient to begin the sintering process. This phenomenon will be
explained in more detail in Fig. 5. When the input voltage is greater
than 40 V, the line patterns are burned and blown out for all the ini-
tial resistance (Fig. 3(c)). This is due to the sudden excessive heat
generation from a higher input voltage. The blowout may be attribut-
ed to the entrapped gas caused by the thermal decomposition of the
organic additives during electrical sintering. The organic additives
are vaporized in the printed line by a rapid temperature increase
due to an input voltage. The vaporized gas pressure increases with in-
creasing the input voltage. At a higher input voltage, an excessive gas
pressure from an excessive heat generation causes the internal gas to
be suddenly exhausted, which could result in burn and blowout of the
printed lines.
In order to further examine the effects of input voltage and initial re-
sistance, we conducted the electrical sintering by varying the input volt-
age from 20 V to 100 V and the initial resistance from 500 to 5 M
when the sintering time is set to 20 s. Fig. 4(a) illustrates the relation-
ship between the input voltage and initial resistance based on the ex-
perimental results that consists of three different regions: sintering,
no change, and blowout. When the initial resistances are too high,
there are no changes in electrical characteristics, i.e. sintering does not
occur even at a higher input voltage. In contrast, the lines are burned
and blownout at the input voltage larger than40 Vin spite of lowinitial
resistances. For the condition of the initial resistance lower than
~100 k and the input voltage ranging from 20 V to 40 V, all the lines
are well-sintered without damaging the underlying photo papers.
Note that, within the sintering region, a higher initial resistance close
to the upper limit requires a higher input voltage.
The initial power consumed in the printed line was also evaluated
to gure out the minimum power to trigger the electrical sintering.
The power can be calculated as a function of time t as follows:
P
l
t
V
2
in
R
l
t R
s

2
R
l
t 1
where P
l
(t) is the electric power in aninkjet-printed line, V
in
is the input
voltage, and R
l
(t) and R
s
are the resistance of the line and the auxiliary
Fig. 3. Effects of (a) applied input voltage and (b) sintering time on the resistance of
electrically sintered patterns. (c) Typical microscopic and FE-SEM images of blowout
of the printed line for an input voltage larger than 40 V.
Fig. 4. Electrical sintering characteristics for (a) various input voltages and initial resis-
tances and (b) various input voltages and initial powers.
159 S. Jang et al. / Thin Solid Films 546 (2013) 157161
series resistance, respectively. The relationship between the input volt-
age and initial power is shown in Fig. 4(b). When the initial power is
lower than 4 mW, no sintering occurs. In order to trigger sintering, at
least 4 mW power is necessary at the beginning stage although the
printed line may be well-sintered or may be blown out.
In the sintering region in Fig. 4(a), the resistance of printed line
varies abruptly with the sintering time during the electrical sintering
instead of decreasing linearly, as shown in Fig. 5(a). At the rst begin-
ning stage, the resistance is the same as the initial resistance, and
then it drops sharply at a specic time. Finally, its value is stabilized
and remains unchanged with time. Actual sintering occurs within a
very short time. Rapid grain growth occurs as the resistance experi-
ences a sudden drop, which makes the printed patterns more conduc-
tive. Note that the sudden drop of resistance occurs at almost the
same time up to a certain initial resistance, but it takes a little longer
before such a resistance drop occurs when the initial resistance is
close to the upper limit. The variation of the power with time calcu-
lated by Eq. (1) is also shown in Fig. 5(b). The power variation has a
tendency opposite to the resistance variation. There is an abrupt
rise in the power at the same time when the resistance begins to
sharply drop, and the peak power, P
peak
, occurs when R
l
= R
s
. The
peak power can be expressed as follows:
P
peak

V
2
in
4R
s
: 2
Since P
peak
is only a function of V
in
and R
s
, it is independent of the
initial resistance, R
l
(0).
In order to investigate the effects of the initial and peak powers
on the sintering characteristics, we conducted another experiment
with two different sets of condition that have the same initial and
peak powers: 1) V
in
= 20 V, R
s
= 0.3 k, and R
l
(0) = 40 k and
2) V
in
= 100 V, R
s
= 7.5 k, and R
l
(0) = 1 M. The results show
that the rst condition produces well-sintered lines, but all the lines
sintered with the second condition are burned and blown out. This
means that the initial and peak powers are not the only factor that de-
termines whether or not the sintering is well done. The sintering
characteristics are also inuenced by the initial resistance. Lower ini-
tial resistances result from denser grain structures, which mean
higher mechanical strength of the printed line. If the initial mechani-
cal strength of the line is sufcient, it is less likely for the line to be
burned or blown out during the electrical sintering. Therefore, the
electrical sintering characteristics seem to be related to both the elec-
trical power and the mechanical strength of printed lines.
The input voltage prole was also changed to improve the sintering
performance. Two-step input voltages of 25 V and 65 V were sequen-
tially applied to the printed line with the initial resistance of 100 k
for 10 s and 5 s, respectively. Fig. 6 compares the grain structures
sintered by one-step input voltage of 25 V with those sintered by
two-step input voltage of 25 V and 65 V. The former's resistance is
~20 while the latter's one is ~4 . The resistance using two-step
input voltage is ve times as small as that using one-step input voltage.
The resistivity value from the two-step sintering is ~3.0 cm, which
is about two times larger than the bulk Ag resistivity. Note that no burn-
ing or blowout is observed in the two-step sintering even though an
input voltage greater than 40 V is applied. This is because the printed
line is already sintered to some extent at rst 25 V input, resulting in
the increase in its mechanical strength. When comparing the grain
structures, the two-step sintering is found to provide bigger grain size
and less void area than the one-step sintering.
Fig. 5. (a) Variation in the resistance of printed lines with sintering time for different
initial resistances and (b) variation in the resistance and the power of printed lines
with sintering time when the initial resistance is 100 k.
Fig. 6. FE-SEM images of (a) the grain structures sintered by one-step voltage of 25 V
for 10 s and (b) the grain structures sintered by two-step input voltages of 25 V and
65 V for 10 s and 5 s, respectively.
160 S. Jang et al. / Thin Solid Films 546 (2013) 157161
4. Conclusion
We have investigated the effects of initial pattern resistance, input
voltage, sintering time, and input voltage prole on the electrical
sintering characteristics of printed line patterns on a photo paper. The
preheating was conducted at a temperature much lower than the ther-
mal sintering temperature to control the initial resistance of patterns.
Whenthe one-stepinput voltage prole is applied, the sintering charac-
teristics are signicantly affected by the input voltage and the initial re-
sistance rather than the sintering time. No sintering occurs for too high
initial resistances whereas all the printed lines are burned and blown
out when the input voltage is larger than 40 V. The electrical sintering
is done well within a short time without damaging the paper substrates
when the initial resistance is lower than ~100 kand the input voltage
is in the range of 20 V and 40 V. The two-step sintering improves the
electrical performance about ve times compared to the one-step
sintering by increasing the grain size and decreasing the void. Since
the electrical sintering has many advantages over the conventional
thermal sintering method, it could be utilized as a fast and reliable
sintering method in practical printed electronics applications.
Acknowledgments
This work was supported by the SW-embedded Device Development
Program(No. 10043828) by the Ministry of Knowledge Economy. It was
also supported by the R&Dprogram(No. S2077231) of the Korean Small
& Medium Business Administration.
References
[1] S. Dasgupta, R. Kruk, N. Mechau, H. Hahn, ACS Nano 5 (2011) 9628.
[2] H. Yan, Z.H. Chen, Y. Zheng, C. Newman, J.R. Quinn, F. Dotz, M. Kastler, A.
Facchetti, Nature 457 (2009) 679.
[3] A. Teichler, R. Eckardt, S. Hoeppener, C. Friebe, J. Perelaer, A. Senes, M. Morana, C.J.
Brabec, U.S. Schubert, Adv. Energy Mater. 1 (2011) 105.
[4] J.U. Park, J.H. Lee, U. Paik, Y. Lu, J.A. Rogers, Nano Lett. 8 (2008) 4210.
[5] T.H.J. van Osch, J. Perelaer, A.W.M. de Laat, U.S. Schubert, Adv. Mater. 20 (2008)
343.
[6] B.J. de Gans, P.C. Duineveld, U.S. Schubert, Adv. Mater. 16 (2004) 203.
[7] J. Perelaer, C.E. Hendriks, A.W.M. de Laat, U.S. Schubert, Nanotechnology 20
(2009) 165303.
[8] H.H. Lee, K.S. Chou, K.C. Huang, Nanotechnology 16 (2005) 2436.
[9] D.J. Lee, S.H. Park, S. Jang, H.S. Kim, J.H. Oh, Y.W. Song, J. Micromech. Microeng. 21
(2011) 125023.
[10] J. Perelaer, B.J. de Gans, U.S. Schubert, Adv. Mater. 18 (2006) 2101.
[11] J. Perelaer, M. Klokkenburg, C.E. Hendriks, U.S. Schubert, Adv. Mater. 21 (2009)
4830.
[12] I. Reinhold, C.E. Hendriks, R. Eckardt, J.M. Kranenburg, J. Perelaer, R.R. Baumann,
U.S. Schubert, J. Mater. Chem. 19 (2009) 3384.
[13] S.H. Ko, H. Pan, C.P. Grigoropoulos, C.K. Luscombe, J.M.J. Frechet, D. Poulikakos,
Nanotechnology 18 (2007) 345202.
[14] S. Magdassi, M. Grouchko, O. Berezin, A. Kamyshny, Acs Nano 4 (2010) 1943.
161 S. Jang et al. / Thin Solid Films 546 (2013) 157161