Microelectronics Reliability 54 (2014) 2871–2880

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Microelectronics Reliability
journal homepage: www.elsevier.com/locate/microrel

Mechanical and environmental durability of roll-to-roll printed silver

nanoparticle film using a rapid laser annealing process for flexible
electronics
Min Yang a, Min-Woo Chon a, Joo-Hyun Kim a, Seung-Hyun Lee b, Jeongdai Jo b, Junyeob Yeo c,
Seung Hwan Ko c, Sung-Hoon Choa d,⇑
a
Department of Mechanics & Design, Kookmin University, Jeongneung-Ro 77, Seongbuk-Gu, Seoul 136-702, Republic of Korea
b
Nano-Mechanical Systems Research Division, Korea Institute of Machinery and Materials, 171 Jang-dong, Yuseong-gu, Daejeon 305-343, Republic of Korea
c
Department of Mechanical & Aerospace Engineering, Seoul National University, Gwanak-Ro 1, Gwanak-Gu, Seoul 151-742, Republic of Korea
d
Graduate School of NID Fusion Technology, Seoul National University of Science and Technology, Gongneun-Ro 232, Nowon-Gu, Seoul 139-743, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: We investigate the mechanical durability and environmental stability of laser annealed silver (Ag)
Received 20 February 2014 nanoparticle (NP) film. Roll-to-roll printed Ag NP film on polyethylene terephthalate substrate is
Received in revised form 29 June 2014 annealed with a rapid laser annealing process in ambient conditions as an alternative to the conventional
Accepted 3 July 2014
thermal annealing process. The laser annealed Ag NP film exhibits superior electrical and mechanical
Available online 14 August 2014
properties, with fast annealing time and no damage on the substrate. The outer/inner bending test results
demonstrate that the flexibility of the laser annealed Ag film is excellent. The failure bending radii in the
Keywords:
outer/inner bending tests are 3 mm. The laser annealed film can withstand 10,000 bending cycles. A
Laser annealing
Silver nanoparticle
nano-scratch test indicates that the adhesion strength of the laser annealed film is comparable to that
Flexibility of the thermal annealed film. The environmental reliability of Ag NP film is investigated under different
Environmental reliability high-temperature and high-humidity conditions, while being subjected to cyclic bending fatigue stress.
The durability of printed Ag film is found to be influenced by temperature and humidity. The laser
annealed film shows relatively large increase in resistance during the bending fatigue test under high
temperature and humidity condition (60 °C/90% RH), which is attributed to the oxidation of Ag nanopar-
ticles and initiation of cracks. Generation of cracks is accelerated owing to the combinational effects of
the cyclic stress and humidity. These results suggest that, even though the laser annealed Ag film dem-
onstrates sufficient mechanical durability, further improvement of the film properties is required for use
in extreme mechanical and environmental conditions.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Printing techniques have received extensive attention for the
mass production of large-area flexible electronics at low cost since
the market for flexible electronics is anticipated to grow rapidly in
the near future. A variety of printing technologies, including ink-
jet, gravure and roll-to-roll (R2R) printing, has developed for the
application of flexible electronic devices, such as solar cells, dis-
plays, thin-film transistors, and printed circuit boards [1–3] owing
to their outstanding throughput and simplicity of process. In print-
ing techniques, metal nanoparticle (NP) inks of gold (Au) or silver
(Ag) are widely used for fabricating conducting lines or electrodes
⇑ Corresponding author.
E-mail address: shchoa@seoultech.ac.kr (S.-H. Choa).
[4,5]. Metal NPs used for printing techniques require an additional
thermal annealing to achieve high conductivity of the printed
metal film [6]. However, conventional thermal annealing process
takes considerable time, and the substrate can be damaged as
the heat is directly applied to it. For application to flexible electron-
ics, the annealing temperature should be as low as possible to min-
imize damage to the flexible polymer substrate (usually under
150 °C). Additionally, conventional thermal annealing processes
are batch processes, and they are difficult to apply in R2R anneal-
ing. Recently, several alternative methods for annealing techniques
have been suggested, such as rapid thermal annealing using a hal-
ogen lamp [7], laser [8,9], infrared [10], intense pulse light [11,12],
plasma [13] and microwave annealing [14]. So far several studies
have focused primarily on the material synthesis, electrical
performance, and microstructure of metal NP films [15,16]. The

http://dx.doi.org/10.1016/j.microrel.2014.07.004
0026-2714/Ó 2014 Elsevier Ltd. All rights reserved.
2872 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880
physicochemical and electrical properties of carbon/polyesteri-
mide thick- conductive film were investigated by Dziedzic
[17,18]. However, there has been very little work on the mechani-
cal durability and environmental reliability of laser annealed NP
film.
The laser annealing process in particular, which has several
advantages, has been emerged as a practical annealing method.
Now it is a primary concern whether the laser annealed NP films
possess good enough mechanical durability and environmental
stability to be used for mass production, as compared to thermal
annealed NP films. Flexible electronic devices will be subjected to
various mechanical deformations, such as bending, compression,
and stretching, depending on their application and fabrication pro-
cesses. The printed NP films should maintain good performances
under severe mechanical deformations. Also repeated bending of
the device during use or the R2R process such as rolling and unroll-
ing will cause cyclic mechanical strains. It is likely a large number
of cyclic strains could eventually cause failure of the film as
reported by Sim et al. [19]. Furthermore, environmental conditions
such as high temperature and humidity have significant effects on
performance and failure of the film. The temperature and humidity
will change the mechanical and electrical properties of the NP film.
High temperature and/or humidity will increase the surface chem-
ical reactions or oxidation on the metal NP film. The natural porous
structure of NP film is vulnerable to the condition of harsh humid-
ity, because it has many voids and micro-cracks. Previous research
has considered the behavior of inkjet-printed Ag ink in humid con-
ditions [20–22], and focused on weakening of the adhesion as the
main failure mechanism. However, the reliability of printed NP
films depends greatly on different inks and substrate materials
used, as well as annealing methods. It is important to characterize
environmental issues for reliable long-term operation, in particu-
lar, the durability of the printed NP film subjected to combined
environmental and mechanical stress. Despite the importance of
environmental reliability for printed electronics, few studies have
been published.
In this study, we demonstrated the rapid laser annealing pro-
cess to anneal R2R printed Ag NP film as a replacement for the con-
ventional annealing process. We then investigated the mechanical
durability of the laser annealed Ag film via outer/inner bending,
stretching, cyclic fatigue, and adhesion tests. The environmental
reliability of Ag NP film was also investigated under different
high-temperature and high-humidity conditions, while being sub-
jected to cyclic bending fatigue stress. The mechanical durability
and environmental stability of the laser annealed Ag film were
compared with conventional thermal annealed Ag film.
2. Experimental details
The Ag nanoparticle paste (ANP DGP-OS12000) was composed
of 66.6 wt% silver nanoparticles ranging from 30 to 50 nm in size,
30–33 wt% solvent (alpha-terpineol and diethylene glycol monobu-
tyl acetate), and 2–3 wt% polymer (epoxy resin). The viscosity was
about 12,000 cps at 0.4 rpm of shear rate (Brookfield viscometry,
CP51 spindle). Ag NP paste was printed on polyethylene terephthal-
ate (PET) substrate (width: 300 mm, thickness: 100 lm, SKC SH34)
by a continuous R2R gravure-offset printing process. As shown in
Fig. 1, R2R gravure-offset printing process is composed of three pro-
cesses, namely the doctoring, off, and set processes [23,24]. The
printing speed was set to 0.6 m/min and the printing force set to
147 N. Usually, the printed pattern is dried for about 2 min at
80 °C by thermal dryer, after which its thickness is about 400 nm.
Fig. 2 shows schematic illustrations of the laser annealing system
and the detailed optical experimental setup. Diode-pumped contin-
uous (CW) Nd:YAG laser (Spectra-Physics, Millennia V) operating at
Fig. 1. Schematic drawing of gravure-offset roll-to-roll printing process and
printing module.
532 nm wavelength is used for laser annealing. The laser beam
passes through half wave plate (HWP) and a polarized beam splitter
(PBS) to change its power. The laser beam is then made to enter to
the scanner (Scanlab, hurrySCAN II) after being expanded five times
by a beam expander (BE). The scanner consists of a telecentric lens
(f = 100 mm) and two galvano mirrors which are controlled by a
computer program (SAMLight). The power and scanning speed of
laser are varied in the ranges of 200–1500 mW and 500–
6000 mm/s, whereas the scanning area and the focused laser spot
size are fixed at 25 mm  25 mm and 15 lm, respectively.
Throughout several preliminary experiments, we found that the
optimal conditions of the laser power and scanning speed were
200 mW and 1000 mm/s, respectively. If the scanning speed was
too high, Ag NPs were not properly sintered or only partially sin-
tered. Also, if higher laser power was exerted, pores and cracks were
observed on the film surface. Generation of these pores is caused by
the large volume reduction during laser annealing when organic
substances are removed, and by sudden evaporation of gases, which
are released suddenly as the organic substances inside the Ag NP
film burn in a very short period of time owing to the high laser
energy. For comparison, conventional thermal annealing was con-
ducted for the Ag NP film at 120 °C for 120 min in a furnace. The
onset temperature for the observable thermal deformation on the
PET substrate was 150 °C. The thermal annealing was therefore
conducted at a relatively mild temperature of 120 °C in order to
prevent any thermal damage on the PET substrate.
The resistance of the films was measured using a digital mul-
timeter (34401A; Agilent), and the four-point probe method was
used to cross-check the resistivity of the films. The thickness of
the Ag NP films was measured using an alpha-step surface profiler
(Tencor P-11). A field emission scanning electron microscope
(FESEM; Hitachi S-4800) was used to analyze surface cracks and
the surface morphology of the Ag NP films, while cross-sectional
images were examined by a focused ion beam (FIB) (SMI3050SE).
The SEM operating voltage was 15 kV.
The mechanical durability of the Ag NP films deposited on the
PET substrate was evaluated via outer/inner bending, stretching,
and cyclic fatigue tests with lab-made testers. Fig. 3 shows the
schematic illustration of the bending test. The bending test was
performed with decreasing bending radius from flat position. Dur-
ing the tests, the electrical resistance was measured in situ using a
multimeter, and the existence of cracks in the films was continu-
 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880
Fig. 2. Schematic drawing of the laser annealing system.
Fig. 3. (a) Schematic drawing of a lab-made bending tester. (b) Outer bending test
with bending radius r.
ously monitored with an optical microscope (OM). The bending
test can be performed by two methods, depending on the stress
on the films. The outer bending test, which bends the sample into
a convex shape (), induces tensile stress on the film, while the inner
bending test, which bends the sample into a concave shape (),
induces compressive stress. As shown in Fig. 3(b), the radius of cur-
vature in the sample is not constant, thus the condition of uniform
curvature may not be available. Here, the configuration of the
buckling beam of the film is regarded as a sinusoidal shape. There-
fore, the actual bending radius (r) of the center of the bent sample
can be approximately calculated using Eq. (1) [25]
L an OM and SEM.
Bending radius ðrÞ ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2ffi ð1Þ
2
2p L  p12Lh2s
dL
where L, dL/L, and hs denote the initial length of the sample, rate of
change of the length, and the substrate thickness, respectively.
Based on Eq. (1), the nominal bending strain of the film can also
be calculated using Eq. (2) [26]:
hf þ hs hs
Strain ffi ffi ð2Þ
2r 2r
where hf denote the film thickness. The cyclic bending fatigue tests
were carried out using a cyclic bending test machine for the dura-
tion of 10,000 cycles, at a frequency of cyclic motion of 30 cycles
2873
per minute. The bending fatigue tester can keep on bending the
sample from plane (1) to specific bending radius for customized
cycle setting. For mechanical durability tests, the sample was cut
to 25 mm  25 mm, and four tests were performed for each sample.
The sheet resistance of the Ag NP film on the PET substrate was
measured to be in the range of 0.5–1.0 X/square for both thermal
and laser annealed samples. Electrical resistivity of Ag NP film
was 20–40  108 X m which is comparable to that of commonly
used Ag inks in R2R gravure printing technologies [7,27,28]. Electri-
cal resistivity of Ag NP film is 12.5–25 time higher than the bulk sil-
ver (1.59  108 X m).
To confirm the environmental stability of the laser annealed Ag
NP film on PET, the environmental reliability tests were conducted
on samples with different temperature and humidity combinations
under the cyclic bending fatigue test. For the different temperature
and humidity conditions, three accelerated tests were performed
according to well-known and widely applied industrial electronics
standards: high temperature of 85 °C, high humidity of 85% rela-
tive humidity (RH), and combined high temperature and high
humidity (60 °C/90% RH) for 10,000 bending cycles. The bending
tester was placed in the environmental chamber with the test sam-
ples. After environmental conditions are stabilized, the bending
tests were performed under high temperature or/and humidity
conditions.
Adhesion between the Ag NP film and the PET substrate could
be an important issue that affects the mechanical properties of
the film and the development of a suitable handling process for
fabrication [29]. Therefore, the adhesion of the Ag NP film on the
PET substrate was qualitatively estimated by a peel-off test using
adhesive tape (3 M Tape™) and a nano-scratch test, respectively.
Scratch tests were performed with a Nano Scratch Tester (CSM
Instruments), using a 2 lm-radius spherical diamond indenter,
which scanned over a 5 mm track. The scratching speed was
5 lm/s with a loading rate of 10 mN/min. The load was ramped
up from the initial 0.3 mN to the final load of 20 mN. The failure
modes that occur at certain critical loads were confirmed using
3. Results and discussion
Fig. 4 depicts the SEM image of the surface morphology of the
Ag NP film on the PET substrate before and after the annealing step.
Before the annealing step, the Ag NP film consists of individual Ag
NPs, which are separated from one another. After the conventional
thermal annealing process at 120 °C for 120 min, the individual
NPs are still discernible, as shown in Fig. 4(a). On the other hand,
after the laser annealing process, the Ag NPs show a relatively
smooth and continuous film structure, as seen in Fig. 4(b) even
though the Ag NPs shows a local ununiformity of surface morphol-
2874 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880

Fig. 4. SEM image of fabricated Ag NP film: (a) before and after thermal annealing; (b) before and after laser annealing.

ogy. Fig. 5 shows the cross-sectional SEM images of both films. For
the thermal annealed film in Fig. 5(a), even though the film shows
rough surface morphology, as seen in Fig. 4(a), it has a densely
packed structure with large columnar grains, and most of the Ag
nanoparticles are fused together with less porosity. The laser
annealed film in Fig. 5(b) also shows a very compact structure,
and the cross-sectional morphology is similar to that observed in
the thermal annealed film. No obvious cracks or voids can be
observed. Also, the figure shows the clear interface between the
film and the substrate without partial melting or damage of the
PET substrate. The absence of thermal damage to the substrate
after the laser annealing process can be explained by several
reasons. First, absorption of the laser happens only at the Ag NP
layer because the laser is selectively absorbed by Ag NPs, not by
the PET substrate, owing to the optical transparency of PET at
532 nm wavelength. And the laser can be more efficiently depos-
ited to the nanoparticle by laser irradiation [9,30] due to surface
plasmon oscillation mode of conduction electrons in the transition

Fig. 5. Cross-sectional SEM images at the interface between the Ag NP film and PET substrate: (a) thermal annealed Ag film; (b) laser annealed Ag film.
 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880
metal nanoparticles and the electric field enhancement between
nanoparticles, which cannot be observed in conventional thermal
annealing. Second, the damage on the substrate can be negligible,
even at a temperature that exceeds the glass temperature of PET,
because the duration of heating for a single spot is very short, in
the order of several tens of ls, owing to the rapid scanning of
the laser spot using the galvano-mirror scanner. These properties
make the proposed laser annealing process suitable for the selec-
tive annealing of the metal NP ink on thermally vulnerable flexible
substrates. In fact, the total processing time for the laser annealing
of the 25 mm  25 mm Ag NP film sample is only 40 s. The laser
processing time can be further reduced by increasing laser power
while maintaining same laser intensity to achieve same degree of
nanoparticle annealing. On the while, it is generally known that
conventional thermal annealing requires an annealing process
time of more than a few hours. Increasing the annealing tempera-
ture is another option, but it is restricted in the conventional bulk
annealing process because of possible thermal damage to the PET
substrate.
Flexibility as a function of the change of bending radius is eval-
uated by measuring the change in electrical resistance. Fig. 6
shows the typical outer bending test results for the laser annealed
Ag film and the thermal annealed Ag film, respectively, with a
decreasing outer bending radius. The change in electrical resis-
tance of the film is expressed as DR(=R  Ro)/Ro, where Ro is the ini-
tially measured electrical resistance and R is the measured
resistance after bending. The outer bending test results demon-
strate that the electrical resistance of the bent laser annealed Ag
NP film does not change until it is bent to a bending radius of
10 mm, which corresponds to a strain of 0.5%. As the bending
radius is further decreased, the electrical resistance gradually
increases. At a bending radius of 3 mm (2.1% strain), there is a
13% increase in the resistance. Bending test results of the thermal
annealed Ag film demonstrate a similar trend to those of the laser
annealed film. At a bending radius of 3 mm, there is an 11%
Fig. 6. Outer bending tests with decreasing bending radius for thermal annealed Ag
film and laser annealed film. The pictures in the upper panel show the optical
microscope images of the bending test at outer bending radii of 1 (flat) and 10 mm,
3 mm, respectively.
2875
increase in the resistance. Owing to the PET substrate thickness
effect, decreasing the bending radius below 3 mm is impossible
in the bending test.
Fig. 7 shows the typical results of the inner bending test when
the inner bending radius for thermal and laser annealed Ag NP
films, respectively, is decreased. For the laser annealed film, the
resistance of the Ag film is constant until the sample is bent to
an inner bending radius of 10 mm. The electrical resistance
decreases slightly at a bending radius of 5 mm, and there is a
10% decrease in the resistance at a bending radius of 3 mm. The
thermal annealed Ag film also shows a trend similar to the laser
annealed film. The electrical resistance slightly decreases at a
bending radius of 5 mm, and there is an 8% decrease in the resis-
tance at a bending radius of 3 mm. The outer/inner bending test
results demonstrate that the bendability of both films is excellent;
in particular, the bendability of the laser annealed Ag film is com-
parable to that of the thermal annealed Ag film.
It should be noted that the electrical resistance increases when
the outer bending radius is increased (or with increasing tensile
strain), while the resistance decreases when the inner bending
radius is decreased (or with increasing compressive strain). The
possible reasons for the increase in resistance during tensile strain
are discussed by several studies [31–33], and can be explained by
different phenomena, such as breaking of the 3D network formed
by the conductive filler particles and loss of contact between differ-
ent nanoparticles. Furthermore, Fig. 8 shows the SEM images of the
cracks in the surface of the laser annealed Ag NP film after the
outer bending test at 3 mm bending radius. The small and short
cracks in the local area are observed on the surface of the film. It
is thought that the existence of the isolated micro-cracks also con-
tributed to a slight increase in the resistance. The thermal annealed
Ag film was also found to have micro-cracks in the local area. For
the inner bending test, the compressive strain contributed to nar-
rowing the 3D network of Ag nanoparticles and increased the con-
Fig. 7. Inner bending tests with decreasing bending radius for thermal annealed Ag
film and laser annealed film. The pictures in the upper panel show the optical
microscope images of the bending test at outer bending radii of 1 (flat) and 10 mm,
3 mm, respectively.
2876 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880
Fig. 8. Surface SEM images with enlarged images of the cracks generated on the
laser annealed Ag film after the outer bending test at the radius of 3 mm.
tact between different particles, which led to the decrease in resis-
tance of the film.
Fig. 9 shows the outer bending fatigue tests for both thermal and
laser annealed Ag films. The bending radius is fixed at 10 mm,
which corresponds to a strain of 0.5%, to prevent failure of the film
before cyclic loading. It was observed that the changes in resistance
throughout 10,000 bending cycles were very small for both films,
and no cracks or delamination were observed. These results demon-
strate the superior flexibility and durability of the laser annealed Ag
film.
A unique feature of the laser annealing process is the laser
annealing mark along the laser scanning direction after the anneal-
ing process, as shown in Fig. 10. This laser annealing mark is
Fig. 9. Cyclic outer bending fatigue tests for thermal annealed Ag film and laser
annealed film.
Fig. 10. Laser annealing mark after laser annealing process for Ag NP film.
caused by the different intensity distribution of a Gaussian beam
and laser spot overlap during the laser scanning process. In order
to investigate whether this laser annealing mark affects the
mechanical durability of the laser annealed film, the uniaxial
stretching test was performed. Fig. 11 shows the stretching test
results for Ag NP films depending on the laser scanning direction.
Fig. 11(a) is the test result of the sample in which the stretching
direction is along the laser scanning direction, and Fig. 11(b) is
for the sample in which the stretching direction is perpendicular
to the laser scanning direction. The trend of the resistance change
is similar for both samples, and the resistance difference between
the two samples is not large. In general, the electrical resistance of
both samples rose slightly from the substrate strain of 1.5%. At 4%
strain, the resistance increased by more than 20%. We also con-
ducted the outer/inner bending tests, depending on the different
scanning direction. The bending tests showed almost the same
results, regardless of the laser scanning direction (not shown in
the figure). These results indicate that the laser annealing mark
did not affect the mechanical durability of the film, but it was
observed that some cracks were propagated along the direction
of the laser mark.
Fig. 12(a) reveals the uniaxial stretching test results for the laser
annealed film and thermal annealed film. As stated above, the elec-
trical resistance of the laser annealed film rose by more than 20% at
the substrate strain of 4%, and the PET substrate was plastically
deformed. SEM analysis of the laser annealed film after the stretch-
ing test, as shown in Fig. 12(b), showed several cracks on the film,
and the film was delaminated from the PET substrate. Meanwhile,
the thermal annealed film showed almost constant resistance until
it was stretched to the substrate strain of 4%, indicating that the
laser annealed film showed slightly inferior stretchability than
the thermal annealed film. Fig. 13 shows the results of the cyclic
bending fatigue tests for the thermal annealed Ag film under three
different accelerated environmental conditions, which are a high
temperature of 85 °C, high humidity of 85% RH at 30 °C, and com-
bined high temperature and high humidity (60 °C/90% RH), respec-
tively. The trend of the resistance change was similar, regardless of
different environmental conditions. The resistance gradually
increased to about 25% over the 5000 cycles, and then remained
almost constant throughout the 10,000 cycle test. After completion
of the test, the thermal annealed Ag film showed an approximately
27% increase in resistance. Fig. 14 shows the results of the cyclic
bending fatigue tests for the laser annealed film under different
environmental conditions. The trend of the resistance change was
similar to that of the thermal annealed film, even though the
increase in resistance was slightly higher than that of the thermal
annealed film. In particular, in the case of combined high tempera-
ture and humidity (60 °C/90% RH), the laser annealed film showed
 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880
Fig. 11. Uniaxial stretching test for laser annealed Ag film: (a) stretching along the
laser scanning direction; (b) stretching perpendicular to the laser scanning
direction.
Fig. 12. (a) Stretching test results for thermal annealed Ag film and laser annealed
Ag film. (b) SEM surface image of the laser annealed film after completion of the
stretching test.
2877
Fig. 13. Cyclic outer bending fatigue tests under different environmental conditions
for thermal annealed Ag film.
an approximately 32% increase in electrical resistance after the test.
The increase in resistance was higher than the bending fatigue tests
conducted in ambient conditions, as shown in Fig. 9. A high increase
in resistance might be attributed to the oxidation of Ag nanoparti-
cles and the crack generation. In particular, an early increase in
resistance was due to the oxidation of Ag NP under high tempera-
ture or high humidity. When the oxide of Ag NP grows thick, oxide
growth is saturated, and the change of resistance remains almost
constant. Fig. 15 shows the typical SEM surface image of the laser
annealed film after the bending fatigue test under 60 °C/90% RH
condition. Several cracks were observed on the surface of the film.
The cracks were much wider and larger, as shown in Fig. 15(a), than
the cracks observed in the bending test performed in ambient con-
ditions, shown in Fig. 7. The FIB cross-sectional image of Fig. 15(b)
shows that the Ag NP film was delaminated from the PET substrate,
and the film was protruded in a convex shape, owing to the combi-
national effects of cyclic tensile stress and humidity. These results
indicate that, even though the annealed Ag films have excellent
mechanical durability, the durability of printed Ag film is reduced
under repeated cyclic stress and high humidity conditions. In par-
ticular, the initiation of micro-cracks is very critical. Once the crack
is initiated, pre-existing cracks trigger larger cracks, owing to the
combinational effects of the cyclic mechanical stress and humidity,
and result in relatively large increase in electrical resistance. There-
fore, void and porosity in the film should be minimized for use in
extreme mechanical and environmental conditions.
Adhesion between the printed film and substrate is an impor-
tant factor, because poor adhesion leads to delamination and low
Fig. 14. Cyclic outer bending fatigue tests under different environmental conditions
for laser annealed Ag film.
2878 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880

Fig. 15. SEM image of the laser annealed Ag NP film after outer bending fatigue test under high temperature and humidity (60 °C/90% RH): (a) typical cracks on the surface of
the film; (b) FIB cross-sectional image of cracks.

Fig. 16. SEM panoramic images of the scratched film and the major scratch failure loads of film at cracking and film delamination: (a) thermal annealed Ag film; (b) laser
annealed Ag film.

reliability of the devices. In this work, the adhesion of the Ag NP
film on the PET substrate was estimated via a peel-off test, using
adhesive tape and a nano-scratch test, respectively. The adhesive
tape was firmly pressed onto the film and slowly peeled off with
a peel-off tester at 180°. Both films did not peel off, and no damage
or delamination was observed on the surface of the films (not
shown in figure). Additionally, the electrical resistance of both
films remained the same after the peel-off test. It was concluded
that both films were mechanically robust and had a reliable
adhesion to the substrate.
The adhesion strength of the films was examined using a nano-
scratch test, to enable a more precise comparison. Fig. 16 shows the
 M. Yang et al. / Microelectronics Reliability 54 (2014) 2871–2880
panoramic SEM scratch morphologies for both films, with the direc-
tion of scratching occurring from left to right. For the thermal
annealed film, shown in Fig. 16(a), initial film cracking was observed
at the applied load of 5 mN. As the scratch load increased, the Ag film
experienced plastic deformation, and there was material accumula-
tion on both sides of the scratch groove of the film. For the laser
annealed film, shown in Fig. 16(b), cracking failure was observed at
3 mN. As the scratch load increased, the film of the scratch track edge
began to be delaminated and brittle film fragments were observed.
This failure mechanism is mainly observed in a hard coating/soft sub-
strate system [34,35]. At a scratch load of 20 mN, the film was com-
pletely delaminated from the substrate. The cracking load of the
laser annealed film was found to be not much different from that of
the thermal annealed film, indicating that the adhesion strength of
the laser annealed film is comparable to that of the thermal annealed
film. However, based on observed failure mode, it seems that the laser
annealed film is more brittle than the thermal annealed film.
Increased brittleness of the laser annealed film may be attributed to
slightly inferior stretchability of the film than of the thermal annealed
film as shown in Fig. 12(a). Therefore, optimization of the laser pro-
cess conditions is required. In conclusion, the laser annealed Ag film
showed sufficient mechanical flexibility and adhesion strength, both
of which are comparable to the thermal annealed film. Dziedzic and
Słobodzian [36] performed the systematic reliability tests including
long-term thermal exposure and moisture exposure tests using Ag
ink films. In this study, we did not consider the long-term stability
and fatigue of the polymer substrate. However, some attention should
be given to thermal fatigue of the polymer substrate, where fracture is
caused by hysteresis heating. Fracture of the polymer substrate will
influence the fracture of Ag NP electrode. Since this study involves
the molecular mechanism and micromechanics, further work is
needed to better understand these effects.
4. Conclusions
In this study, high-speed laser annealing was employed for
annealing the Ag NP film, as an alternative to conventional thermal
annealing. The mechanical durability of the laser annealed Ag film
deposited onto a PET substrate was investigated via outer/inner
bending, stretching, cyclic fatigue, and adhesion tests, and com-
pared to those of the thermal annealed Ag film. The environmental
stability of Ag NP film was also investigated under different
high-temperature and high-humidity conditions, while being sub-
jected to cyclic bending fatigue stress. In the laser annealing pro-
cess, the Ag NP film underwent instantaneous annealing upon
exposure to the laser exposure, so that the sheet resistance fell
immediately under 1 X/square within a few seconds. The laser
annealed Ag film showed superior flexibility. The failure bending
radii in the outer/inner bending tests were 3 mm. The bending fati-
gue test showed that the laser annealed film can withstand 10,000
bending cycles, and the nano-scratch test indicated that the
adhesion strength of the laser annealed film is comparable to that
of the thermal annealed film. The cyclic bending fatigue tests under
different environmental conditions demonstrate that the durabil-
ity of the printed Ag film is influenced by temperature and humid-
ity. The increase in resistance is higher than that of the bending
fatigue tests conducted in ambient conditions. In particular, in
the case of combined high temperature and high humidity, both
films showed a large increase in resistance, as well as delamination
of the film. A large increase in resistance may be attributed to the
oxidation of Ag nanoparticles and crack growth. The cracks are
generated owing to the combinational effects of the cyclic mechan-
ical stress and high humidity. These results suggest that, even
though the laser annealed Ag film demonstrated sufficient
mechanical durability, film properties should be further improved
2879
for use in extreme mechanical and environmental conditions. In
particular, void and porosity in the film should be minimized.
Acknowledgments
This study was supported by a grant from the cooperative R&D
Program (B551179-10-01-00), funded by the Korea Research Coun-
cil Industrial Science and Technology, and the R&D Program,
‘‘Development of a reliability test for small/mid-sized flexible dis-
play,’’ funded by the Ministry of Trade, Industry & Energy, Republic
of Korea.
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