Combined Role of Well-Dispersed Aqueous Ag Ink and the Molecular Adhesive Layer in

Inkjet Printing the Narrow and Highly Conductive Ag Features on a Glass Substrate
Sunho Jeong,* Hae Chun Song, Won Woo Lee, Youngmin Choi, Sun Sook Lee, and
Beyong-Hwan Ryu*
DeVice Materials Research Center, Korea Research Institute of Chemical Technology, 19 Sinseongno, Yuseong,
Daejeon 305-600, Korea
ReceiVed: July 27, 2010; ReVised Manuscript ReceiVed: October 13, 2010
A novel inkjet printing procedure based on a well-dispersed aqueous Ag ink and a molecular adhesive layer
is presented for the fabrication of highly conductive and narrow patterns exhibiting the excellent adhesion
property on a glass substrate. The aqueous dispersion of silver nanoparticles is synthesized via a chemical
reduction method in the aqueous medium in which an anionic polyelectrolyte is incorporated as both a capping
agent and a dispersant. Owing to the electrosteric repulsion characteristic of the anionic polyelectrolyte, the
prepared aqueous Ag ink exhibits the long-term dispersion stability. A molecular adhesive layer is deposited
on a glass substrate using either aminopropyltriethoxysilane or mercaptopropyltriethoxysilane. The distinctive
functional group of the molecular adhesive layer plays a critical role in the adhesion property as well as high
contact angle appropriate for forming the narrow Ag patterns, which is achieved only with the aqueous ink.
It is demonstrated that the resulting inkjet-printed Ag patterns with a line width of 45 m exhibit the excellent
adhesion property and resistivity as low as 3.7 cm, after annealing at temperatures ranging from 200 to
300 C.
1. Introduction
In recent years, the direct printing of functional materials has
attracted increasingly signicant interest as large-area and low-
cost processing techniques for the fabrication of conductive
features on a transparent glass substrate in modern electronic,
opto-electronic, and photovoltaic applications. Despite the wide
adoption of photolithography in the microfabrication of conduc-
tive features, its complicated process signicantly increases
manufacturing costs and poses major obstacles to realize modern
large-area and inexpensive electronics.
1,2
In particular, inkjet
printing, which can deliver precise quantities of materials to
desired locations, has been regarded as an alternative to
conventional lithography.
3-9
To date, Ag nanoparticles have been studied as promising
functional materials for conductive inks since they exhibit high
conductivity (10
5
S/cm), operational stability, and low-
temperature processability.
4,5,8
As the size of the metal particles
decreases below a few tens of nanometers, the melting point
abruptly falls due to their high surface energy, and the sintering
process, which is essential to form a conductive dense layer,
takes place at a low temperature compatible to a glass substrate.
Nevertheless, inkjet printing of conductive Ag ink on a glass
substrates has been little studied because of its tendency to
spread widely on a glass substrate and the poor adhesion
property of printed Ag patterns. Recently, Jang et al. reported
that the addition of glass frit, which can melt at elevated
temperatures as high as 600 C, enables the printed Ag patterns
to adhere well to a glass substrate.
10
However, the melting of
glass frit requires relatively high-temperature annealing, and the
conductivity of printed Ag patterns signicantly degrades the
more that glass frit is added. In addition, the spreading problem
was not resolved, resulting in the printing of the wide Ag pattern
with a line width of 150 m.
To overcome such drawbacks, we have incorporated the
molecular adhesive layer composed of self-assembled molecules
and utilized DI water as a dispersant medium for Ag nanopar-
ticles. The use of solvent with high surface tension as a
dispersion medium aids in obtaining the liquid-solid interface
with a high contact angle required to form narrow printed
features. Recently, the salt-based aqueous ink was reported for
printing Ag conductive lines on the polyimide substrate.
However, despite optimization of process conditions, the
conductivity of the Ag pattern was limited to 27 cm.
11
In
comparison with particle-based ink, the active material in a salt-
based ink is partially composed of organic residues which should
be thermally decomposed at elavated temperature, which
deteriorates the microstructure of the printed pattern and in turn
electrical property. To date, Ag nanoparticles have been,
however, synthesized in the nonaqueous medium,
12-15
whereas
noble metal nanoparticles such as Au, Pt, and Pd have been
successfully synthesized in the aqueous medium.
16,17
The Ag
nanoparticles synthesized in organic medium are hardly dis-
persed in the aqueous medium since most capping agents, which
are used to control particle size and prevent interparticular
agglomeration, are inactive in the aqueous medium. Therefore,
for the development of aqueous Ag ink, the surface-capping
molecules should be replaced with water-compatible molecues,
or Ag nanoparticles should be synthesized in aqueous medium
with capping molecules which can be active in aqueous
medium.
18-20
In addition, the aqueous ink allows the use of
polyelectrolyte as both a capping agent and a dispersant, which
gives rise to electrosteric repulsion,
21
enabling a suspension with
long-term dispersion stability.
22
In the case of nanoparticles
synthesized in organic medium, most capping molecules exhibit
relatively weak steric repulsion, so that the sophisticated design
* To whomcorrespondence should be addressed. E-mail: sjeong@krict.re.kr
(S.J.); bhryu@krict.re.kr (B.-H.R.).
J. Phys. Chem. C 2010, 114, 2227722283 22277
10.1021/jp106994t 2010 American Chemical Society
Published on Web 12/01/2010
on surface chemistry is essential to achieve the long-term
dispersion stability.
In this study, we report remarkably well-dispersed aqueous
Ag ink containing the polyelectrolyte-capped Ag nanoparticles
and the noble way to enhance the adhesion property of printed
Ag patterns using the adhesive layer composed of self-assembled
molecules. We demonstrate that the combination of well-
dispersed Ag ink and the molecular adhesive layer facilitates
the inkjet-printed Ag patterns with excellent adhesion property,
high conductivity, and narrow line width.
2. Experimental Section
2.1. Materials. All reagents, silver nitrate (AgNO
3
, 99%),
sodium borohydride (NaBH
4
, 99%), poly(acrylic acid) (PAA,
[CH
2
CH(CO
2
Na)]
n
, 35 wt % in H
2
O, M
w
)15 000), ammonium
hydroxide (NH
4
OH, 25%), nitric acid (HNO
3
, 60%), 3-ami-
nopropyltriethoxysilane (APTES, H
2
N(CH
2
)
3
Si(OC
2
H
5
)
3
,
99%), and 3-mercaptopropyltriethoxysilane (MPTES, HS
(CH
2
)
3
Si(OC
2
H
5
)
3
, 95%), were purchased from Aldrich and used
without additional purication. Hydrazine (NH
2
NH
2
, 80%) was
purchased from Daejung Chemicals & Metals and used without
additional purication.
2.2. Ink Preparation. Ag nanoparticles were synthesized via
chemical reduction of Ag ions in DI water. To prevent the
interparticular agglomeration, poly(acrylic acid) (PAA) was
incorporated as a surface-capping molecule, and a mixture of
hydrazine and sodium borohydride was used as a reducing agent.
Amounts of 25.5 g of Ag nitrate, 14.9 g of poly(acrylic acid),
and 1.5 g of a mixture of hydrazine and sodium borohydride
were added into a three-neck, round-bottomed ask containing
100 mL of DI water. The ask was tted with a reux
condenser. After reaction for 80 min at 25 C, the synthesized
Ag nanoparticles were selectively separated by a centrifugation
method, and obtained Ag nanoparticles were washed with DI
water by centrifugation for 40 min under 68 470g. For prepara-
tion of the Ag conductive ink, Ag nanoparticles were dispersed
in DI water with the solid loading of 25 wt %, and the pH of
aqueous Ag ink was adjusted by adding either diluted NH
4
OH
or HNO
3
.
2.3. Preparation of the Glass Substrate with Molecular
Adhesive Layer and Inkjet Printing. A bare glass substrate
was cleaned subsequently with Piranha solution (H
2
O
2
:H
2
SO
4
) 3:7), DI water, acetone, isopropyl alcohol, ethyl alcohol, and
DI water and dried with an N
2
stream. Either 3-aminopropyl-
triethoxysilane (APTES) or 3-mercaptopropyltriethoxysilane
(MPTES) was deposited by immersing a clean bare glass
substrate in a mixture of silane, ethyl alcohol, and DI water.
The volumeric ratio of ethyl alcohol to DI water was 19, and
the concentration of silane was 2 vol %. Then, the Ag conductive
ink was printed on a bare, APTES-treated, and MPTES-treated
glass substrate. The substrate temperature was maintained at
25 C. The printer set up is composed of a drop-on-demand
piezoelectric inkjet nozzle manufactured by Microfab Technolo-
gies, Inc. (Plano, TX), and the diameter of the orice is 30 and
50 m. The inkjet-printed Ag nanoparticulate lms were
annealed at various temperatures from 100 to 350 C for 60
min in ambient atmosphere.
2.4. Characterization. The size and shape of the synthesized
Ag nanoparticles and the microstructures of Ag patterns
annealed at different temperatures were observed by scanning
electron microscopy (SEM, JSM-6700, JEOL). The crystal and
chemical structure of Ag nanoparticles were analyzed using an
X-ray diffractometer (XRD, D/MAX-2200 V, Rigaku) and
X-ray photoelectron spectroscopy (XPS, K-Alpha, Thermo
Figure 1. (a) SEM image of particulate lm composed of Ag nanoparticles. The inset is a TEM image of synthesized Ag nanoparticles. (b) The
particle size distribution of synthesized Ag nanoparticles. The measured average particle size is 19.5 nm.
Figure 2. (a) XRD pattern and (b) XPS spectrum of synthesized Ag nanoparticles. Two peaks in the XPS spectrum, which is located at 368.1 and
374.1 eV, correspond to Ag 3d
5/2
and 3d
3/2
binding energy, respectively. In comparison with Ag
0
(368.3 and 374.3 eV), the peaks shift down to
lower binding energy, indicating that the chemical environment around Ag atoms is changed due to capping molecules.
22278 J. Phys. Chem. C, Vol. 114, No. 50, 2010 Jeong et al.
Fisher Scientic). The XPS spectrum was collected using
monochromatic Al KR radiation (1486.6 eV) in an ultrahigh
vacuum system with a base pressure of 10
-10
Torr. The surface
charge was measured with a zeta-potential analyzer (ELS-Z,
Otsuka). Rheological behavior of prepared Ag conductive ink
was monitored using a modular compact rheometer (MCR 101,
Anton Paar) at shear rates ranging from 10
-1
to 10
3
s
-1
and a
capillary viscometer (Online viscometer VROC, Rheosense) at
shear rates ranging from 10
3
to 10
5
s
-1
. The contact angle was
measured with a dynamic contact angle system (SEO 300, SEO),
and the thermal decomposition behavior of the PAA adsorbed
on the particles was monitored using thermal gravimetric
analysis (SDT2960, TA Instruments). The morphology and
resistivity of the printed Ag patterns were analyzed using a
surface proler (Alpha-step IQ, KLATencor) and four-point
probe station equipped with a semiconductor characterization
system (Keithley 4200, Keithley), respectively. The adhesion
property of printed Ag lines was characterized according to the
ASTM D3359 standard test method based on tape testing.
Printed lines with the length of 2 cm were cut 2 mm apart with
a razor blade. A piece of 3M 610 tape was placed over the
prepared sample and rubbed rmly with an eraser for good
contact between the tape and sample. Then, the tape was
removed by seizing the free end as close to an angle of 180 as
possible, and the fraction of the remaining area was inspected
by observing the resulting printed features using an optical
microscope.
3. Results and Discussion
3.1. Preparation of Well-Dispersed Aqueous Ag Ink and
Inkjet Printing on a Bare Glass Substrate. We synthesized
Ag nanoparticles by reducing the Ag ions in the aqueous
medium in which poly(acrylic acid) (PAA) was dissolved. As
shown in Figure 1, the size of the synthesized Ag nanoparticles
was measured as 20 nm with a small deviation, and the
nanosized monodispersed particles allowed the formation of a
highly packed particulate lm. In addition, according to XRD
and XPS analysis, it is revealed that the synthesized Ag
nanoparticles consist of a pure Ag phase without secondary
phases such as byproduct or oxide phases, as shown in Figure
2.
In our synthesis method, PAA plays a critical role as
a capping agent to control particle size and shape as well as a
dispersant to give rise to electrosteric repulsion. PAA is a
polymer with an ionizable functional group (COONa), which
dissociates to produce charged polymers. These charged poly-
mers lead to electrosteric repulsion, involving a combination
of electrostatic repulsion and steric repulsion. The degree of
repulsion in electrosteric stabilization is much higher than that
in a single electrostatic or steric stabilization. The dissociation
rate is strongly dependent on the pH of the aqueous medium. It
has been known that the fraction of the dissociated group is
1 in the aqueous medium with pH > 6, and the degree of
dissociation gradually diminishes as the pH of the aqueous
medium decreases (the degree of dissociation is nearly zero in
the aqueous medium with pH < 3).
18
We measured the zeta-
potential to analyze the surface charge induced by the dissociated
groups and its dependence on pH of the aqueous medium (Figure
3a). As expected, the high zeta-potential greater than -50 mV
evolved at pH > 6, and the zeta-potential decreased slightly at
pH of 4.8 due to the slightly incomplete dissociation; the surface
charge was nearly zero at a pH of 2.5. Thus, it is speculated
that the dispersion of Ag nanoparticles in the aqueous medium
with pH > 4.8 would be governed by strong electrosteric
repulsion, yielding the superior dispersion stability.
As shown in Figure 3b, PAA-capped Ag nanoparticles
dispersed well in the aqueous medium with pH > 4.8 without
incorporating any additional dispersants. The dispersion stability
of the prepared ink has been monitored for more than two
months, and no precipitates have been observed yet. Further
investigation on long-term dispersion stability is ongoing. On
the contrary, Ag nanoparticles in ink prepared using the aqueous
medium with pH of 2.5 were precipitated 120 min after ink
preparation. This different dispersion characteristic was also
conrmed in rheological behavior. As shown in Figure 3c, Ag
ink prepared using the aqueous medium with pH > 4.8 exhibited
Newtonian behavior with a shear rate of 10
5
s
-1
(since the shear
rate around 10
4
10
5
s
-1
is applied in the nozzle during inkjet
Figure 3. (a) Zeta-potential of Ag nanoparticles as a function of pH
of an aqueous medium. (b) Gravitational sedimentation test for Ag inks
prepared using the aqueous medium with different pH. This test was
carried out to determine the degree of particle agglomeration by
observing the volumes of suspension zone. As the particles in the
unstable suspension agglomerate and settle, the volume of the suspen-
sion zone decreases. (c) Rheological behavior of Ag inks prepared using
the aqueous medium with different pH. The viscosity of ink containing
agglomerates (pH 2.5) was not measured at shear rates ranging from
10
3
to 10
5
s
-1
due to capillary-tube clogging. In the case of well-
dispersed Ag ink (pH > 4.8), reliable viscosity data were not obtained
at a low shear rate below 10 s
-1
due to the extremely low torque value.
Role of Aqueous Ag Ink & Molecular Adhesive Layer J. Phys. Chem. C, Vol. 114, No. 50, 2010 22279
printing, the monitoring on rheological property in this range
is very important), indicative of a well-dispersed suspension.
If particle aggregation occurs, the inks shows shear-thinning
behavior, which is characterized by a gradual decrease in
apparent viscosity with increasing shear rate.
23
The increase in
the shear rate breaks down the aggregates, which leads to a
reduction in the amount of solvent immobilized by the particles,
thus lowering the apparent viscosity of the system.
24
Shear-
thinning behavior could be observed in well-dispersed suspen-
sions containing asymmetric particles. However, since the
synthesized Ag nanoparticles were spherical in shape, it is
presumed that the shear-thinning behavior is attributed only to
the formation of agglomerates.
Such well-dispersed ink allowed the use of a nozzle with a
small orice diameter, which aids in forming the narrow printed
patterns. If the metal nanoparticles are not well-dispersed, it is
difcult to eject the stable droplets through the nozzle with an
orice diameter smaller than 30 m since the nozzle is easily
clogged, and even if the droplet is successfully ejected, its
stability would be poor. The image and dimensions of droplets
ejected through a nozzle with orice diameters of 50 and 30
m are shown in Figure S1 and Table S1 (Supporting Informa-
Figure 4. Thermal gravimetric analysis curves of (a) PAA and (b-d) Ag nanoparticle: (b) thermal behavior as a function of temperature ranging
from 25 to 400 C, (c) thermal behavior as a function of annealing time at 200 C, and (d) thermal behavior as a function of annealing time at 200
C. The number in red in (c,d) indicates the fraction of decomposed PAA.
Figure 5. (a) Molecular structure of APTES and MPTES. (b) Comparison of adhesion property (based on ASTM D3359 tape test) of Ag line
patterns printed on bare, MPTES-treated, and APTES-treated glass substrates. The number on top of the bar indicates the annealing temperature.
The orice diameter of the nozzle used here was 30 m.
22280 J. Phys. Chem. C, Vol. 114, No. 50, 2010 Jeong et al.
tion). The line widths of Ag patterns printed using nozzles with
diameters of 50 and 30 m are 100 and 65 m, respectively
(Figure S2, Supporting Information), which represents that the
line width of printed patterns linearly decreases as a function
of the volume of the jetted droplets.
The as-printed Ag pattern consists of resistive particulate
layers, which are converted to conductive dense layers by a
thermally activated sintering process. The sintering process is
also involved in the temperature-dependent decomposition of
PAA adsorbed to Ag nanoparticles since the sintering process
occurs by diffusion of Ag atoms into the boundary area between
neighboring particles and capping molecules act as a barrier
layer against atom diffusion. According to the analysis on a
thermal decomposition of PAA (Figure 4a), the weight loss
below 140 C is attributed to the evaporation of solvent (DI
water) and adsorbed solvent molecules, and the weight loss
above 400 C is assigned to the thermal decomposition of PAA.
Therefore, when the surface of Ag nanoparticles was surrounded
by PAA, it is suggested that the solvent molecules adsorbed to
PAA present in the surface of the Ag nanoparticle evaporate
below 140 C, and the weight loss above 140 C is mainly due
to the thermal decomposition of PAA, as shown in Figure 4b.
The shift of temperature at which PAA is decomposed results
from the catalytic effect of the Ag nanoparticle.
25,26
On the basis
of the fraction of decomposed PAA at 200 and 250 C (this
value was calculated using the ratio of weight loss at a specic
temperature, obtained from either Figure 4c or 4d, to total weight
loss observed in Figure 4b), it is believed that the thermal
decomposition of PAA surrounding Ag nanoparticles partially
took place at 200 C and was completed at 250 C, which
indicates that interparticular growth begins at 200 C. This is
in line with the fact that the resistivity of the printed Ag pattern
drastically decreased at 200 C to 4.1 cm (Figure S3,
Supporting Information). However, the printed Ag pattern
annealed at 200 C completely peeled off after the adhesion
test (see Experimental Section for details).
3.2. Inkjet Printing of Well-Dispersed Aqueous Ag Ink
on a Glass Substrate with a Molecular Adhesive Layer. To
improve the adhesion property, we introduced the molecular
adhesive layer via depositing either aminopropyltriethoxylsilane
(APTES) or mercaptopropyltriethoxysilane (MPTES), which
consists of three alkoxy groups and one distinctive functional
group. The molecular structures of APTES and MPTES are
depicted in Figure 5a. Alkoxy groups react with the hydroxyl
groups present in the surface of the glass substrate, and either
the amine group in APTES or the thiol group in MPTES is
chemically bonded to the Ag nanoparticle. It has been well-
known that the thiol group is strongly chemisorbed on the Ag
surface by the formation of a covalent-like bond between the
silver and the sulfur atoms, and the binding of a silver
nanoparticle to an amine group arises from the silvers ability
to donate electrons to the nitrogens antibonding orbital via
back bonding.
27-32
As shown in Figure 5b, the adhesion property
of the printed Ag pattern after annealing at 200 C was
drastically improved on ATPES-treated glass. However, in the
case of MPTES-treated glass, the adhesion property of the
printed Ag pattern appeared to be relatively poor and thermally
vulnerable above 250 C. While Ag printed patterns adhered
well to the amine-functionalized glass substrate even after
annealing at 300 C, the adhesion property of Ag patterns printed
on the thiol-functionalized glass substrate signicantly deterio-
rated after annealing at 250 C. This different behavior was
believed to relate to molecular-structural thermal stability of
the adhesive layer, so that we analyzed the variation of contact
angles as a function of annealing temperature to elucidate the
origin for this different behavior (Figure 6). The contact angle
of DI water on the amine-functionalized glass substrate did not
vary signicantly at temperatures ranging from 25 to 300 C
and abruptly fell after annealing at 350 C, which is in
accordance with the adhesion property tendency. Therefore, it
is presumed that the degradation of the adhesion property in
the Ag patterns printed on the amine-functionalized glass
substrate was due to the thermal decomposition of APTES. On
the contrary, in the case of the thiol-functionalized glass
substrate, the variation in the contact angles and adhesion
properties as a function of annealing temperature did not agree
well with each other. While the contact angle abruptly fell after
annealing at 300 C, the adhesion property degraded after
annealing at 200 C. It has been reported that a desorption of
Figure 6. Variations in the contact angle of DI water on MPTES-
treated and APTES-treated glass substrate as a function of annealing
temperature.
Figure 7. (a) Resistivity of Ag line patterns as a function of annealing
temperature. The orice diameter of the nozzle used here was 30 m.
(b) SEM images showing the microstructural evolution of Ag line
patterns annealed at the indicated temperatures. The scale bar is 1 m.
The insets are high-magnication SEM images, and the scale bar is
500 nm.
Role of Aqueous Ag Ink & Molecular Adhesive Layer J. Phys. Chem. C, Vol. 114, No. 50, 2010 22281
alkanethiolate adsorbed on Au takes place through cleavage of
the Au-S bond over the range of 170-220 C,
33-36
and most
thiol-derived self-assembled molecules supported on silver show
some qualitative resemblance to properties observed in assembly
on gold.
27-29
In addition, it was reported that the benzenethi-
olates are desorbed from the silver surface below 200 C, not
undergoing the structural changes.
37
Thus, it is speculated that
the cleavage of the Ag-S bond took place around 200 C prior
to the thermal decomposition of the MPTES itself at 300 C,
resulting in a relatively poor adhesion property at 200 C and
complete peel-off at 250 C. This implies that the thiol-
functionalized adhesive layer is not acceptable as an adhesive
layer for conductive printed features activated by annealing
above 200 C.
Figure 7a shows the variations in resistivity of the Ag pattern
printed on the APTES-treated glass as a function of annealing
temperature. As the annealing temperature increases to 200 C,
the resistivity of the printed pattern drastically decreased,
exhibiting resistivity as low as 3.7 cm, and the resistivity
did not change at temperatures ranging from 200 to 300 C.
This dependence of resistivity on annealing temperature is
associated with the aforementioned thermally driven sintering
process, which was conrmed by the structural evolution as a
function of annealing temperature (Figure 7b). The individually
isolated Ag nanoparticles were interconnected by a sintering
process at 200 C at which the resistivity reaches the value
comparable with the resistivity of bulk Ag. The resistivity of
3.7 cm was 2.3 times larger than the resistivity of bulk
Ag, which is attributed to the presence of small voids generally
observed in the printed patterns. It should be noted that given
the resistivity of Ag patterns printed on a bare glass substrate
the amine-functionalized adhesive layer did not deteriorate the
electrical property of the upper conductive line. However,
resistivity abruptly increased after annealing at 350 C, which
results from the microstructural collapse caused by the thermal
decomposition of the underlying self-assembled adhesive layer
(Figure 8).
3.3. Role of Aqueous Ag Ink in Printing the Narrow
Conductive Features. In addition to its role in improving the
adhesion property, the molecular adhesive layer facilitated a
narrow printed pattern. Once the self-assembled adhesive layer
is deposited, the surface of the glass substrate is functionalized
by either an amine or a thiol group, which leads to the lower
surface energy compared with a hydroxyl-terminated bare
substrate. The surface energy of the top layer, which is in contact
with Ag ink during the printing process, predominantly deter-
mines the contact angle of the Ag ink. After the deposition of
the self-assembled adhesive layer, the contact angle effectively
increased above 40 (Figure 9). In general, the high contact angle
below 50 facilitates the formation of the narrow printed pattern
since the diameter of the printed dots diminishes inversely with
the contact angle and dots printed on the substrate with a contact
angle above 50 cannot merge uniformly into a line feature.
Note that other self-assembled adhesive layers do not enhance
the adhesion property because of the lack of chemical-bonding
nature with Ag atoms and cannot also satisfy the contact-angle
criterion for narrow printed features (for instance, the contact
angle of Ag ink on the glass substrate treated with hexameth-
yldisilazane and octadecyltrichlorosilane was 75 and 98,
respectively). As shown in Figure 10, the narrow inkjet printed
Ag feature with the line width of 45 m was obtained on
APTES-treated glass, and the complex Ag patterns were also
successfully printed on a large-area APTES-treated glass
substrate. On the other hand, in the case of nonaqueous ink,
this distinctive role of self-assembled adhesive layer is not
active. Organic solvents such as ethanol, toluene, hexane,
chlorobenzene, and tetradecane, which are commonly used in
nonaqueous metal inks, have a low surface tension (the surface
tension of each solvent is summarized in Table 1), so that the
substrate surface energy is not capable of acting as a determining
factor for the contact angle. As shown in Figure 9, all
nonaqueous solvents tested in this study showed extremely
hydrophilic wetting behavior.
Figure 8. Cross-sectional proles of (a) nonannealed Ag line pattern and Ag line patterns annealed at (b) 250 and (c) 350 C. All line patterns
were printed on APTES-treated glass substrate, and the orice diameter of the nozzle was 30 m.
Figure 9. Contact angle of Ag ink and several solvents on bare,
MPTES-treated, and APTES-treated glass substrates. The inset images
show the wettability of Ag ink on each substrate.
Figure 10. Optical microscope image for Ag complex patterns printed
on the large-area APTES-treated glass substrate. The orice diameter
of the nozzle was 30 m, and the dot spacing was 40 m. The inset
shows an optical microscope image for a printed Ag single line.
22282 J. Phys. Chem. C, Vol. 114, No. 50, 2010 Jeong et al.
To the best of our knowledge, this study represents the rst
attempt to directly write highly conductive and narrow Ag
patterns that adhere well to a glass substrate at a low temper-
ature. The noble way described here, which is based on the
combination of a self-assembled adhesive layer and remarkably
well-dispersed aqueous Ag ink, is expected to provide a
convenient and low-cost method for fabricating conductive
features which can be adopted in various elds including modern
electronics, opto-electronics, and photovoltaic applications.
4. Conclusions
We prepared aqueous Ag ink with long-term dispersion
stability using monodispersed Ag nanoparticles synthesized in
the aqueous medium in which PAA was incorporated as a
capping agent as well as a dispersant. We also deposited the
self-assembled adhesive layer on a glass substrate to enhance
the adhesion property of printed Ag features, and it was
demonstrated that the amine-functionalized adhesive layer acted
well as a thermally stable adhesive layer at temperatures ranging
from 25 to 300 C. The combination of aqueous ink and
molecular adhesive layer enabled the narrow printed features
and superior adhesion property without degrading the electrical
property of the printed Ag features, resulting in a line width of
45 m and resistivity as low as 3.7 cm.
Acknowledgment. This study was supported by a grant
(B551179-08-03-00) from the cooperative R&D Program funded
by the Korea Research Council Industrial Science and Technol-
ogy and carried out for the Direct Nano Patterning Project
(TS091-45) supported by the Ministry of Knowledge Economy
under the National Strategic Technology Program.
Supporting Information Available: The images and physi-
cal dimensions of jetted droplets, images of the Ag pattern
printed on a bare glass substrate, and resistivity variation as a
function of annealing temperature. This material is available
free of charge via the Internet at http://pubs.acs.org.
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JP106994T
TABLE 1: Surface Tension of Various Solvents Tested in
This Study
surface tension (mN/m)
DI water 72.8
ethanol 22.4
toluene 27.9
hexane 18.4
chlorobenzene 33.6
tetradecane 26.5
Role of Aqueous Ag Ink & Molecular Adhesive Layer J. Phys. Chem. C, Vol. 114, No. 50, 2010 22283