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ABDULLAH 2018020
Abstract
This work demonstrates three=step sintering for inkjet-printed copper thin films. The proposed process
of sequential low-pressure drying near-infrared sintering and intense pulsed light (IPL) reduction ensure
high nanoparticles compactness, complete Cu sintering and low oxygen respectively followed by
enhanced adhesion between Cu and substrate. Cracks from IPL due to differential thermal expansion
were quantified which was the reason for degraded electrical performance for Cu thin films that has
been made beyond optimal condition.
1. Introduction
Inkjet printing for flexible and organic electronic devices has been widely proposed and demonstrated
for its high production efficiency, operational simplicity, low material waste, and high compatibility with
roll-to-roll and continuous manufacturing systems. Although inks based on other metals, such as nickel
[1], iron [2], and aluminum [3] have been also proposed as alternatives and are available on the market,
only Ag [4-6] and Au [7-9] are practical for electrical connections because of their stability during
preservation and manufacturing but they are too expensive.
In practice, heat [10], microwave [11-12], plasma [13] near infrared (NIR) [14], electric current [15], and
laser [16] sintering methods have been proposed for various nanoparticles but all of them are
conducted in ambient air at atmospheric pressure; these methods are not desirable because they tend
to leave potentially resistive Cu-O in the Cu thin films. Consequently, consecutive sintering after inkjet
printing must remove these functional chemicals and connect the Cu nanoparticles to form a continuous
thin film.
Intense pulsed light (IPL) [17-20] has been proposed for low temperature and short-duration Cu
sintering, but incomplete IPL sintering often produces cracks and delamination in Cu thin films that limit
maximal achievable conductivity [19-21]. Even though the cracks and delamination may be alleviated by
series of multiple IPL exposures, in which small amounts of IPL energy are applied for preheating before
more IPL energy is applied for sintering, IPL-only sintering inevitably limits the applications of Cu
nanoparticles if the contributions of IPL to preheating, sintering, and reduction are not quantified.
Although numerous studies have used IPL for all phases, the present study uses a sequential three-step
procedure of ink drying, nanoparticle sintering, and Cu-O reduction by low-pressure ambient air, NIR
exposure, and IPL exposure, respectively, and studies have implied that Cu resistivity can be suppressed
below 15% [21] but it involves bulk resistivity and nanoparticle porosity [22–23]. However, these studies
did not consider oxygen content and cracks in thin films; the conclusions were only applicable to oxygen
and crack-free conditions.
2. Experimental
Because the continuity between and the density of the nanoparticles seriously influence the
electrical performance of Cu, the inkjet-printed sample was put in a customized low-pressure
chamber for drying at 25 °C for 6.5 min to increase the compactness of the Cu nanoparticles.
Although the drying process took 6.5 min to reach 10 kPa in this work, it was limited by the current
facility.
NIR is not suitable for sintering every metal, but this technique is suitable for Cu sintering because
its intensity spectrum efficiently covers the energy absorption spectrum of Cu. As a result, we used
NIR (Adphos, NIR42–125) to sinter the Cu nanoparticles completely and to avoid the previously
discussed selective surface solidification in IPL-only sintering.
The Cu nanoparticle ink that contains photoreactive polymers were decomposed to CH3OH (g),
CH2H5OH (g), C3H7CHO (g), CH3COOH (g), HCOOH (g) by thermodynamic reactions [25–26].
Consequently, Cu was reduced from Cu2O with these decomposed functional groups and all gaseous
byproducts generated in the thermodynamic reactions simply disappear in the environment. Studies
have already disclosed the chemical reactions in the Cu nanoparticle ink when exposed to IPL, in
which Cu oxide together with the protection and surfactant polymers received localized thermal
energy higher than 1290 K. IPL contains a wide intensity spectrum with strong energy, and it is
efficient for breaking the bonds between Cu and O [17–19] to realize high Cu conductivity.
2.5. Characterization
Throughout this work, surface roughness, element content, Cu thin film (both cross-sectional and
top-view) observation, and structure porosity was characterized by surface profiler (Veeco, Wyko
NT1100), energy-dispersive X-ray spectroscopy (EDS; FEI, Helios Nano lab 600i), secondary electron
microscopy (SEM; FEI, Helios Nano lab 600i), and image operation from SEM, respectively. With the
help of setting a threshold of brightness, the areas that were not occupied by Cu nanoparticles or
thin film were identified by ImageJ. By extracting the identified areas and divided it by the complete
area, the porosity and crack ratio were obtainable. The electrical conductivity was obtained from the
sheet resistance and the thickness of the Cu thin film, which was available by the four-point probe
system (Keithley, 2400) and SEM, respectively. The monochrome SEM images of interest was
converted to 8-bit grayscale by ImageJ (National Institutes of Health, version 1.45 s) before they
were enhanced in contrast.
3. Result
Because the inkjet-printed Cu thin film was composed of nanoparticles of various sizes, the low
pressure helped the small nanoparticles to fill spaces between large nanoparticles, producing
improved surface roughness and reduced porosity in the Cu thin films; these films were examined
by image operations that have been used in similar works [14,17,22]. A sample dried under identical
temperature and duration but at 101 kPa had a surface roughness of 36.1 nm; the as-dried
morphology of the 10 kPa-dried Cu thin film showed 65.7% surface roughness reduction from 36.1
to 12.4 nm (Fig. 1(a) and (b)). EDS analysis showed that low-temperature-dried samples had low
oxygen content (Fig. 1(f) and 1(g)) and the suppression of the reactions
between Cu and O was efficient and substantial at raised temperatures (Fig. 1(h) and 1(i)).
The porosity of the Cu thin film was reduced from 38.3% to 24.0% by NIR sintering (45 s), indicating
a 37.3% reduction; this NIR sintering was effective compared to the NIR sintering of Ag nanoparticles
[14], for which porosity reduction was less than 11%. Furthermore, the compactness of Cu
nanoparticles increased after NIR exposure (porosity reduction, Fig. 2(a)) but reduced after thermal
treatment (degraded surface roughness, Fig. 1(d)), indicating a practical sintering in NIR. However,
the reduced Cu content after NIR exposure [(Fig. 2(b), 88.3%) and (Fig. 2(c), 82.2%)] indicated a
resistive thin film, and the elimination of oxygen content [(Fig. 2(b), 4.9%) and (Fig. 2(c), 12.2%)] was
required. The porosity of the Cu thin film abruptly decreased (Fig. 2(a)) and the Cu nanoparticles
grew aft er being cumulatively exposed (45 s, Fig. 2(a) inset).
With these two advantages, the Cu resistivity decreased to a minimum of 7.9 × 10−8 Ω-m with an IPL
energy of 20 J/cm2 (2500 μs exposure), which corresponds to 21.3% conductivity of bulk Cu. As
shown in Fig. 3(a), the oxygen content was reduced from 12.2% to 0%, assuring an oxygen-free Cu
thin film after extensive IPL exposure. As a result, the porosity of the Cu thin film further reduced
from 24.0% to 6.3% as the IPL intensity increased.
4. Discussion
The lowest resistivity achieved in this work was limited to films with large nanoparticle diameters (on
average larger than 70 nm) and did not surpass the results of numerous studies [18,22,26–29], which
used inks with different physical and chemical properties. and we believe that lower Cu resistivity
(higher conductivity) could be achieved with the same progressive sintering if nanoparticle size were
further reduced [30]. standard in this work because Cu nanoparticles were sintered completely through
the thin film by NIR instead of sintered selectively on the top of the thin film by IPL, where Cu loosely
attached to the substrate with remaining solvents in IPL-only sintering
Serious cracks appeared on the surface of the Cu thin films when extensive IPL exposure was applied
and the cracks grew larger as the IPL intensity increased (Fig. 3(b)–(d)). In the present research, the
optimized conductivity still reached the same order of magnitude as that of bulk Cu; the films produced
in this research are eligible for electronic applications. In contrast to NIR, IPL delivered energy not only
to Cu but also to PI and thus produced different thermal expansions in Cu and PI.
5. Conclusion
This work not only proved that good Cu conductivity was achievable in inkjet printing but also clarified
the contributions of individual steps in the proposed procedure: the surface roughness, porosity, and
oxygen content in the Cu thin film were improved 65.7%, 37.3%, and 91.7%, respectively, in the film
with the highest conductivity.
The three steps of this procedure improve the compactness of nanoparticles, the completeness of
nanoparticle sintering, and the effectiveness of Cu-O reduction, respectively. Compared to other works
that paid attention on chemical formulation advancement, which might encounter reliability and
repeatability challenges in mass production and commercialization, we believe that the proposed
sintering procedure is efficient for the users who could only obtain Cu nanoparticle inks from the
market. The surface roughness of the Cu thin film was suppressed to less than 15 nm, which is highly
desirable for electrodes used in organic light emitting diodes and other printed electronic devices.
6. Acknowledgement
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