Research Article

Cite This: ACS Appl. Mater. Interfaces 2019, 11, 7123−7130 www.acsami.org

Electroless Deposition-Assisted 3D Printing of Micro Circuitries for

Structural Electronics
Sanghyeon Lee,†,∥,⊥ Muhammad Wajahat,†,‡,⊥ Jung Hyun Kim,†,‡ Jaeyeon Pyo,† Won Suk Chang,†
Sung Ho Cho,∥ Ji Tae Kim,§ and Seung Kwon Seol*,†,‡
†
Nano Hybrid Technology Research Center, Korea Electrotechnology Research Institute (KERI), Changwon-si,
Gyeongsangnam-do 51543, Republic of Korea
‡
Electrical-Functionality Materials Engineering, Korea University of Science and Technology (UST), Changwon-si,
Gyeongsangnam-do 51543, Republic of Korea
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§
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Department of Mechanical Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong, China
∥
Department of Electronics and Computer Engineering, Hanyang University, Seoul 04763, Republic of Korea
*
S Supporting Information

ABSTRACT: Three-dimensional (3D) printing is a next-generation free-form

manufacturing technology for structural electronics. The realization of structural
electronic devices necessitates the direct integration of electronic circuits into 3D
objects. However, creating highly conductive, high-resolution patterns in 3D
remains a major challenge. Here, we report on a metallic 3D printing method that
incorporates electroless deposition (ELD) into the direct ink writing method. Our
approach consists of two steps: (1) direct ink writing of catalyst microstructures
with a functional catalyst ink containing Ag ions and (2) ELD of Cu onto the
printed catalyst structures. High-quality, stable Cu 3D printing is achieved through
the design of the Ag catalyst ink; hydroxypropyl cellulose is added as both a
rheological modifier (printing) and dissolution inhibitor (ELD). As a result, various
two-dimensional (2D) and 3D Cu micro circuitries with high conductivity (∼65%
of bulk) can be directly integrated onto 3D plastic substrates without the need for
high-temperature annealing. A hybrid strategy that combines ELD-assisted 3D printing and conventional fused deposition
modeling enables full fabrication of structural electronic devices. This 3D printing strategy can be a low-cost and facile method
for obtaining highly conductive metallic 2D and 3D microstructures in structural electronics.
KEYWORDS: 3D printing, structural electronics, electroless deposition, silver catalyst inks, copper

■ INTRODUCTION
Structural electronics is an emerging field that enables the
direct integration of functional electronic circuits on three-
dimensional (3D) devices, in response to the growing demand
for personalized and smart products.1−3 The advancement of
structural electronics provides different and better ways of
implementing electronic functionalities into products. A variety
of electronic componentssuch as conductive traces,
antennas, sensors, transistors, batteries, and so oncan be
directly embedded into 3D devices without the need for
implementing large printed circuit boards (PCBs), load-
bearings, or protective structures.1−8
The creation of highly conductive fine patterns on nonflat,
3D architectures is central to the implementation of structural
electronic devices. This has typically been achieved by the
printing of conductive inks composed of metal nanoparticles
and polymeric stabilizers.9−13 However, these methods
invariably require a high-temperature sintering process to
attain the desirable conductivity of the printed patterns
through the decomposition of the organic stabilizers and the
sintering of metal nanoparticles, which limits printing on light-
weight, flexible polymeric substrates, because they can be
damaged by heat.
Electroless deposition (ELD) is an alternative approach for
obtaining highly conductive metallic patterns on substrates. It
offers a low-temperature, cost-effective, external field-free,
chemical method for metal deposition on insulating sub-
strates.14−17 Practically, the ELD process has been applied to
realize 3D-molded interconnect device (3D-MID) technology
for structural electronics. The 3D-MID process (1) forms 3D
objects via plastic injection molding of a thermoplastic resin
including catalysts (such as Ag or Pd) and (2) metallizes
selective positions by laser direct structuring and ELD.18−21
Laser scanning activates the metallic catalysts on the surface,
and the subsequent ELD process creates conductive patterns.
The 3D-MID process can extend the range of classical PCBs to
3D boards, allowing structures with electrical circuits routed
over any 3D surface to be produced. However, it is difficult to
Received: October 18, 2018
Accepted: January 25, 2019
Published: January 25, 2019

© 2019 American Chemical Society 7123 DOI: 10.1021/acsami.8b18199

ACS Appl. Mater. Interfaces 2019, 11, 7123−7130
ACS Applied Materials & Interfaces Research Article

Figure 1. (A) Schematic illustration and FE-SEM images demonstrating ELD-assisted 3D printing via two successive steps: direct ink writing of
ELD catalyst structures with aqueous functional Ag catalyst inks and selective Cu metallization via ELD. (B) Schematic illustrating the binding
mechanism between Ag ions and APTMS-modified HPC and variation in the FT-IR spectra with the addition of APTMS-modified HPC into the
Ag ink. (C) Viscosity vs shear rate and (D) storage and loss moduli vs ink shear stress. (E) Printability of the ink and structural stability depending
on the presence or absence of HPC in the ink. All inset scale bars represent 1 mm.

fabricate 3D structures with complex shapes because shielded
areas cannot be illuminated by the laser, and the catalyst
cannot be activated.
To tackle this, 3D printing (also known as additive
manufacturing) is emerging as an alternative manufacturing
technology for realizing structural electronics. 3D printing has
typically been focused on producing of 3D architectures with
reliable mechanical properties, making it difficult to obtain
functional circuitries by this method.22−24 However, recent
advancements in 3D printing approaches allow the production
of 3D structures that are both geometrically and electrically
functional.1,25−27 Several attempts that combine ELD metal-
lization and conventional 3D printing methods to fabricate
conductive 3D structures have been reported. First, a method
that combines stereolithography (SLA) and ELD has been
exploited to create metal-coated 3D polymeric structures.28−30
SLA is based on a two-photon absorption technique and offers
spatial resolution down to a few hundred nanometers, making
it a powerful technique for the production of complex 3D
polymeric structures with metallic catalysts for ELD. However,
the use of photo-curable polymers as supporting materials is
essential, which limits the process and its wide application in
electronics. Other studies include the fabrication of thermo-
plastic 3D structures including metallic catalysts via fused
7124
deposition modeling (FDM).31−33 However, the FDM still
suffers from insufficient printing resolution and uniformity.
In this work, we develop an ELD-assisted 3D printing
approach based on direct ink writing to fabricate highly
conductive two-dimensional (2D) and 3D Cu microstructures
with a spatial resolution of ∼10 μm on 3D-shaped substrates.
Our approach consists of two steps: (1) direct ink writing of
Ag catalyst structures with a functional Ag catalyst ink and (2)
ELD of Cu on the printed catalyst structures. The specially
designed Ag catalyst ink includes silver nitrate (AgNO3), 2-
aminopropyltrimethoxysilane (APTMS), and hydroxypropyl
cellulose (HPC). HPC is crucial for the ink design, as it has a
low critical solution temperature (LCST) of 45 °C in water
and therefore maintains the shape of the printed structure
during the ELD step at a reaction temperature of 60 °C.
Importantly, metallized Cu 3D microstructures were obtained
by simply adding supporting materials such as graphite and
alumina into the Ag catalyst ink. Several structural electronic
applications are successfully demonstrated by hybrid 3D
printing that combines our ELD-assisted 3D printing and
conventional FDM.
DOI: 10.1021/acsami.8b18199
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ACS Applied Materials & Interfaces Research Article

■ RESULTS AND DISCUSSION

Figure 1A depicts our ELD-assisted 3D printing technique. It
Cu(L)2 + 2HCHO + 4OH−
→ Cu + 2HCOO− + H 2 + 2H 2O + 2L−
consists of two steps: (1) direct ink writing of ELD catalyst
structures with aqueous functional Ag catalyst inks and (2) where L represents the complexing agents.
selective metallization of Cu on the printed catalyst structures Figure 1E shows the printability of the ink and the stability
via ELD. Precise engineering of the Ag catalyst ink is needed to of the printed structure depending on the presence or absence
achieve uniform and stable catalyst structures. First, the of HPC in the ink. 2D straight lines with Ws = 10 μm were
rheological property of the ink should satisfy its continuous drawn at room temperature on a polyimide (PI) substrate.
and uniform extrusion through a micronozzle and maintenance Uniform line structures were obtained with the ink containing
of the shape of the printed structure. Second, once printed, the HPC via a continuous ink flow through the micronozzle (Dn =
catalyst structures must retain their shapes without dissolution 10 μm). However, in the absence of HPC, the ink flow was
during the ELD solution at a temperature of ∼60 °C. To unstable, yielding nonuniform line structures. Furthermore, we
satisfy these two requirements, we added HPC into aqueous confirmed that HPC aided retention of the shape of the
Ag catalyst ink. HPC acts both as a rheological modifier during printed catalyst structure during the ELD process, enabling the
the printing and as a dissolution inhibitor during the ELD formation of a uniform metallized Cu line.
process. Importantly, the LCST of HPC in water is 45 °C The electrical properties of printed structures are very
between room temperature and the ELD temperature of 60 important for electronic device applications. Figure 2A
presents the dependence of the electrical resistivity of a 5
°C. Therefore, the HPC solution is miscible at room
mm long Cu-metallized line (Ws = 10 μm) on the ELD
temperature and enables a continuous ink flow in a
reaction time at 60 °C. After 1 min of ELD, 2D Cu line
micronozzle,34,35 resulting in uniform printing at the micro-
showed high resistivity of 4.8 × 10−4 Ω·cm because of the
scale. The printed Ag-HPC structures retain their shapes at
during subsequent ELD process in a 60 °C solution bath. (see
Figure S1 and Movie S1 in the Supporting Information). To
link Ag ions and HPC, the surface of HPC is modified with
APTMS.
The binding mechanism between Ag ions and APTMS-
modified HPC is described in Figure 1B. APTMS has an
amino (−NH2) group and three ethoxy (−OCH3) groups. The
ethoxy group is hydrolyzed by water to form a silanol group.
Then, the silanol groups of APTMS form Si−O−Si bonds with
the hydroxyl (−OH) group on the HPC surface, resulting in
the surface modification of HPC with amino functional group.
This conversion can be confirmed by Fourier transform
infrared (FT-IR) analysis. As APTMS is added to the aqueous
HPC solution at room temperature, the intensity of the peak of
hydroxyl groups (at 3427 cm−1) decreases and peaks of −Si−
O−Si− groups (at 1030 cm−1) and amino groups (at 3359 and
3303 cm−1) appear. After adding AgNO3 into the APTMS-
modified HPC solution, the two peaks corresponding to the
amino group are downshifted to 3339 and 3284 cm−1,
respectively, owing to electron donation from the amino
groups to Ag ion,36−38 This change indicates that Ag ions bind
strongly to APTMS-modified HPC.
Figure 1A shows the field emission scanning electron
microscopy (FE-SEM) images of 2D catalyst microstructures
with a width (Ws) of 10 μm. The word “PRINTING” was
obtained by meniscus-guided printing39−49 with the aqueous
Ag catalyst ink at room temperature. The ink has appropriate
rheological properties for reliable flow through the micronozzle
(diameter of the nozzle opening, Dn = 10 μm) (see Movie S2
in the Supporting Information). At 8 wt % HPC, a printable
ink with a viscosity of ∼677 mPa·s was obtained (at a shear
rate of 10 s−1), exhibiting shear-thinning behavior (see Figure
1C). The storage (G′) and loss (G″) moduli of the inks with
and without HPC are shown in Figure 1D. All of the inks Figure 2. (A) Electrical resistivity of Cu-metallized 2D lines as a
exhibited fluid-like behavior (i.e., G′ < G″) as a function of the function of ELD time. Inset: FE-SEM images showing the
morphological changes in the printed lines after 1 and 20 min of
shear stress. During the printing process, the catalyst ink was
ELD. White arrow indicates the deposited Cu on the printed catalyst
supplied continuously through the micronozzle without line. (B) Resistance change of the Cu-metallized lines (Ws = 10 μm;
clogging. After dipping the printed catalyst structure into a length = 5 mm) under long-term storage tests at 25 and 85 °C over 27
Cu ELD solution, Cu was deposited on the catalyst structure days. (C) Simple tape-test to verify the adhesion of the Cu-metallized
via the following reactions50,51 2D structure to the PI substrate.

7125 DOI: 10.1021/acsami.8b18199

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loose connection of the deposited Cu particles (left inset image
in Figure 2A). As the reaction time increased, the resistivity
decreased because of the uniform deposition of Cu on the
printed catalyst line. Well-deposited Cu exhibiting electrical
resistivity of 3.2 × 10−6 Ω·cm was obtained after a reaction
time of 20 min (right inset image in Figure 2A). As the ELD
time increased further, the resistivity remained almost
constant.
We also tested the stability of the metallized Cu structures
against oxidation by monitoring the variation of the resistance
at 25 and 85 °C over 27 days (Figure 2B). Although the
resistance of the Cu lines increased with the storage time
owing to oxidation, the increase did not exceed 10% over 27
days because an oxidative layer formed on the surface, which
prevented oxygen penetration into the line.
Figure 2C shows the results of a tape-test for evaluating the
adhesion between the 2D Cu structure and the PI substrate. A
“KERI” light-emitting diode (LED) sign, consisting of 36 LED
lamps, could be switched on using a Cu structure with saw-
toothed shape (Ws = 10 μm and total length = 4 mm). After
removing the adhesive tape, the Cu structure still functioned as
an electrical interconnector without falling off the substrate,
thus indicating good adhesion (see Movie S3 in Supporting
Information).
Printed Cu 2D structures may be used as electrodes and
electrical interconnects in various devices. To demonstrate this,
we produced a transparent conductive grid composed of
periodic Cu lines (Ws = 10 μm) on a 500 μm-thick
polycarbonate (PC) substrate. The printed Cu grid has an
overall dimension of 1 × 1 cm and a center-to-center line
spacing of 275 μm (Figure 3A and Movie S4 in the Supporting
Information). The Korean alphabets were clearly visible
Figure 3. (A) Optical and FE-SEM images of a Cu-metallized 2D grid
with the electrode feature of 15 μm and center-to-center line spacing
of 275 μm on a PC substrate. LED sign “KERI” is switched on using
the Cu grid as a transparent conductive grid. (B) Optical
transmittance of bare PC (89.1%) and Cu grid printed on PC
(80.2%). (C) Optical images of an automatic LED switch system
composed of an LED, photoresistor, transistor, and two resistors using
Cu-metallized interconnectors (Ws = 20 μm) on a curved PMMA
substrate (curvature radius = 4.8 cm). Inset in the first panel: Circuit
design for the automatic LED switch system. Right panel shows that
the LED on/off can be controlled depending on the ambient light.
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underneath the printed Cu grid. The sheet resistance of the
Cu grid on the PC substrate is 13.46 Ω/□, resulting in
switching-on of the “KERI” LED sign. Figure 3B shows the
transmittance spectra of the bare PC and Cu-grid-printed PC
substrate. The transmittance of the PC substrate with the Cu
grid is 80.2% in the entire visible region, which is only ∼9%
lower than that of bare PC (89.1%). An automatic LED
switching system responding to ambient light was also
implemented on a curved substrate (Figure 3C). To fabricate
the electronic circuit, a Cu line with Ws = 20 μm was printed
on poly(methyl methacrylate) (PMMA) dome structures
(curvature radius = 4.8 cm). Various circuit components
such as LED, photoresistor, transistor, and two resistors were
mounted on the printed Cu circuit. In darkness, the
photoresistor exhibited a high resistance, inducing enough
voltage at the base of the transistor to turn the transistor on,
and therefore turning on the LED. In contrast, the resistance of
the photoresistor was decreased by increasing the incident light
intensity, which induced a low voltage, and turned off the LED.
Thus, the LED switching in the printed system could be
controlled according to ambient light intensity (Movie S5 in
the Supporting Information).
3D patterning of highly conductive metallic structures on
nonflat or 3D substrates is essential for advanced applications
of structural electronics. Cu-metallized 3D structures were
printed via ELD-assisted 3D printing by simply adding
supporting materials into the Ag catalyst ink. The supporting
material changed the viscosity and other rheological properties
of the Ag catalyst ink, thus facilitating the formation of 3D
objects. Figure 4A shows the viscosity (inset) and moduli as a
function of the shear rate and shear stress for a catalyst ink
containing 25 wt % of graphite powder as the supporting
material. In contrast to the rheological property of the Ag
catalyst ink, which had fluid-like behavior (see Figure 1D), the
graphite−Ag catalyst ink exhibited a specific rheological
property with transitions (shear yield stress = 3000 Pa)
between solid-like (G′ > G″) and fluid-like (G′ < G″)
behaviors with respect to the applied shear stress. Such a
rheological property is suitable for an extrusion-based 3D
printing, allowing the fabrication of 3D catalyst structures.
A catalyst 3D grid structure (80 layers, 5 mm cube) with a
wall thickness of ∼200 μm was printed in a layer-by-layer
manner by extrusion-based 3D printing of the graphite−Ag
catalyst ink (Figure 4B). For layer-by-layer deposition, the
micronozzle was moved along determined paths under applied
pressure, with vertical movement (∼62.5 μm) of the nozzle
(Movie S6 in Supporting Information). As the ELD time
increased from 0 (as-printed) to 20 min, the color of the
exterior wall of the 3D grid changed noticeably from black to
metallic brown, owing to the growth of Cu grains on the 3D
grid surface (Figure 4C). After an ELD time of 20 min, the
average grain size at the exterior and interior walls of the 3D
grid increased significantly (larger than 280 nm), thus forming
a continuous network of large grains. We also investigated the
electrical properties of the Cu-metallized 3D grid as a function
of the ELD time (Figure 4D). Current−voltage (I−V) curves
were acquired by probing the exterior and interior walls of the
3D Cu grid. The resistance of the 3D grid clearly decreased as
the ELD time increased. Further, the 3D Cu grid could be used
to activate an LED sign, as shown in the inset photograph of
Figure 4D (Movie S7 in the Supporting Information). The X-
ray diffraction pattern in Figure 4E reveals the crystal structure
of the metallized 3D Cu grid with respect to the ELD time.
DOI: 10.1021/acsami.8b18199
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Figure 4. (A) Rheological properties of graphite−Ag catalyst ink used
for printing Cu-metallized 3D microstructures. The graphite−Ag ink
transitions from a solid-like fluid to a liquid-like fluid as a function of
the shear stress. (B) Optical image of the extrusion-based printing of a
3D grid structure of the catalyst (a cube with a side-length of 5 mm).
(C) Optical and FE-SEM images showing the morphological changes
of the Cu-metallized 3D grids as a function of ELD time. (D) I−V
characteristics of the 3D grid with respect to ELD time. Inset: Optical
image showing the 3D grid used as an electrical interconnector to
activate a LED sign “KERI.” (E) XRD patterns of the Cu-metallized
3D grid as a function of ELD time. As ELD time increases, the
intensity of Cu peak increases. Black dot and purple asterisk indicate
graphite and Cu, respectively.
The XRD peaks are attributed to graphite [black dots: (100),
(101), (102), and (004) planes] and Cu [purple asterisk:
(111) and (200) planes]. We clearly confirmed that the peak
intensity of Cu increased as the amount of deposited Cu
increased with increasing ELD time. Apart from graphite,
various others materials can be used as supporting materials;
the result of using alumina powder as the supporting material
is presented in Figure S2 in the Supporting Information
Figure 5A shows the printing of Cu interconnects on a 3D
polylactice acid (PLA) substrate with different step angles
between 90° and 140°. The height of the step between the top
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Figure 5. (A) Optical images of Cu interconnectors printed on a 3D
PLA substrate with different step angles of 90° and 140°. Images of
(B) “KERI-signal” and (C) “KERI-watch” fabricated using a custom-
made hybrid 3D printing system consisting of ELD-assisted 3D
printing and FDM. Various electrical components were mounted on
the printed electrical circuit.
and bottom plate was kept constant at 3 mm. The PLA
substrate and Cu interconnectors were printed using a custom-
made hybrid 3D printing system consisting of ELD-assisted 3D
printing and FDM. A 15 mm-line with Ws = 1 mm was printed
on the PLA substrate with a step angle of 140° (left image of
Figure 5A). The graphite−Ag catalyst ink has sufficiently high
yield stress to maintain the shape of the 2D line on the sloped
side wall. In the conventional inkjet printing method, the
printing of a continuous line between the top and bottom plate
is limited to structural substrates with step angles larger than
110°.52 As shown in the right panel of Figure 5A, layer-by-layer
printing of 3D structures enabled us to print a 3D interconnect
(height of 3 mm) on the substrate with a step angle of 90°.
We successfully demonstrate the implementation of a
“KERI-signal” and a “KERI-watch” using the hybrid 3D
printing system. The KERI-signal consisted of structural
objects and an electrical circuit including Cu interconnects
(Ws = 200 μm), LEDs, and a resistor (Figure 5B). All of the
3D structural objects were printed using an FDM system with
a PLA filament and Cu interconnects were formed by the
ELD-assisted 3D printing of the graphite−Ag catalyst ink.
Then, the electrical components were mounted on the printed
electrical circuit. Using the same process, we also fabricated a
DOI: 10.1021/acsami.8b18199
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KERI-watch consisting of Cu interconnects, an organic LED
(OLED) display, three switches, two resistors, a battery, and a
microprocessor chip (Figure 5C and Movie S8 in the
Supporting Information).
■
CONCLUSIONS
We demonstrated the fabrication of highly conductive 2D and
3D Cu microstructures on a 3D substrate by 3D printing based
on ELD via direct ink writing of ELD catalyst structures with
aqueous functional catalyst inks and subsequent ELD of Cu.
The key factor for successful ELD-assisted 3D printing is to
tailor the rheological property of the Ag catalyst ink to achieve
continuous ink extrusion and to retain the shape of the printed
catalyst structures. In particular, the printed catalyst structure
must maintain its shape without dissolution in a solution path
at a temperature of ∼60 °C during the ELD process. In our
approach, HPC with a low LCST of 45 °C was added to the
Ag catalyst ink. The HPC functions as a rheological modifier in
the printing process and dissolution inhibitor in the ELP
process. Beyond 2D patterns, 3D microstructures were realized
by the addition of supporting materials such as graphite and
alumina. The Cu-metallized structures exhibited high electrical
conductivity of ∼3.8 × 105 S cm−1, which is ∼65% that of bulk
Cu. We fabricated an automatic LED switching system that
responded to the surrounding light, consisting of a LED,
photoresistor, transistor, electrical resistors, and Cu inter-
connect on a curved substrate (curvature radius = 4.8 cm).
KERI-signal and KERI-watch were also successfully demon-
strated using a hybrid 3D printing technique that combined
our ELD-assisted 3D printing and FDM. Our ELD-assisted 3D
printing technique offers a minimalist and effective way to
obtain high-resolution conductive metal structures for 3D
printed structural electronics.
■
METHODS
Preparation and Characterization of the Catalyst Ink. The
ELD catalyst ink for 2D microstructures was prepared by adding
AgNO3 (0.1 g; 99.8%, Samchun Chemical Co., Ltd., Guaranteed
Reagent grade) to a solution of HPC (1.8 g; 99%, Mw ≈ 100 000,
Sigma-Aldrich) and APTMS (0.1 g; 97%, Sigma-Aldrich) in deionized
(DI) water (8 mL) at 25 °C. The ELD catalyst ink for printing 3D
microstructures was prepared by mixing graphite powder (2.9 g;
99.9999%, ∼75 μm, Alfa Aesar, high purity) with a mixture of HPC (2
g), APTMS (1 g), and AgNO3 (1.15 g) in DI water (4.45 mL) at 25
°C in a mixer (ARE-310; THINKY Cor.). The rheological properties
of the inks were evaluated using a rheometer (MCR102, Anton Paar)
with a cone-and-plate geometry. Variations in the storage and loss
moduli of the catalyst inks were recorded as a function of sweep stress.
Printing. According to the rheological properties of the catalyst
inks, two different printing methods were used: (1) meniscus-guided
printing was performed by exploiting the meniscus formed at the tip
of a glass micronozzle filled with the fluid-like ink. Glass nozzles with
opening diameters (Dn) of ∼10 and 20 μm were obtained using a
nozzle puller (P-97; Sutter Instruments). The ink was filled from the
backside opening of the micronozzle and extruded though the front
tip by capillary forces without applying pressure. The printing speed
and initial gap between the nozzle and the substrate was set at 25 μm
s−1 and 1 μm in all cases, respectively. (2) Extrusion-based printing of
3D microstructures was conducted using a fluid dispenser (Ultimus V,
EFD Inc.). The graphite−Ag catalyst ink, which exhibited solid-like
behavior owing to the added graphite powder, was packed into a
syringe (3 mL barrel, EFD Inc.) and extruded through a micronozzle
(Dn = 200 μm) under applied pressure (Pa = 28 psi). The printing
speed was set at 1 mm·s−1. In both printing approaches, the
micronozzle position was accurately controlled using three-axis
stepping motors with 250 nm positioning accuracy. The nozzle
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motion corresponding to the print paths was designed using a
parameterized G-code scripts. The printing process was observed in
situ using a high-resolution monitoring system consisting of an optical
lens (10× or 200×) and a charge-coupled device camera (Spot RT
Xplore).
ELD of Cu. An ELD solution was prepared by dissolving CuSO4·
5H2O (0.67 g; 99.5%, Samchun Chemical Co., Ltd., Guaranteed
Reagent grade), NaOH (0.8 g; 98%, Daejung Chemical Co.,
Guaranteed Reagent grade), potassium sodium tartrate tetrahydrate
(2.04 g; 99%, Kanto Chemical Co., Extra Pure grade), and
formaldehyde (3 mL; 35%, Daejung Chemical Co., Extra Pure
grade) in DI water (100 mL). To evaporate water from the printed
structures, the specimens were dried in an oven at 100 °C under
atmospheric pressure. Cu ELD was performed at 60 °C by immersing
the printed specimens in an ELD solution. The metallized specimens
were rinsed with DI water and dried in air at room temperature.
Characterization. The microscopic characteristics of the printed
structures were analyzed by FE-SEM (S4800, Hitachi). The
mechanism of Ag ion deposition on the APTMS-modified HPC
was analyzed by FT-IR spectrometry (Nicolet iS10, Thermo
Scientific). The electrical resistivity was measured using a two-probe
method with a Keithley 2612A instrument at room temperature. The
optical property of the transparent conductive grid was compared
with that of bare PC and printed Cu grids on PC via UV−vis
spectrophotometry (Agilent Cary 5000, Agilent Tech.). XRD patterns
(2θ = 40°−55°) were recorded at room temperature at a scanning
speed of 0.15° min−1 using Cu Kα radiation (λ = 0.154 nm) from a 40
kV X-ray source (X’Pert PRO MPD, Philips) operated at 100 mA.
3D Printed Electronic Devices. For the implementation of an
automatic LED switching system including an LED (1005 SMD LED,
Everlight Electronics., Ltd.), photoresistor (GL5537, LONGSAN),
transistor (2N3904, ON Semiconductor), and resistors (2012-
WR08W, NTREX), Cu interconnects were printed on a PMMA
dome structure (curvature radius = 4.8 cm) by ELD-assisted 3D
printing. Meanwhile, KERI-signal and KERI-watch were produced
using a custom-made hybrid 3D printing system consisting of ELD-
assisted 3D printing and FDM. First, the structural bodies were
fabricated by FDM with PLA filaments. Then, Cu-metallized
structures were drawn on the printed 3D PLA structures by ELD-
assisted 3D printing. Various electrical components such as LEDs
(1005 SMD LED, Everlight Electronics., Ltd.), resistors (2012-
WR08W, NTREX), OLED display (SSD 1306 OLED, Arduino), tact
switches (EST-1177, Eastern Electronics), and microprocessor chip
(ATtiny85 Vm, Atmel FSC, Inc.) were mounted on the printed
electrical circuit.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b18199.
Effect of HPC as a dissolution inhibitor, ELD-assisted
3D printing of Cu-metallized 3D structure with alumina-
Ag catalyst, and Tape-test for evaluating the adhesion
between printed patterns and polymer substrates (PDF)
Movie S1: Effect of HPC as dissolution inhibitor
depending on the temperature of water (25 and 60
°C) (AVI)
Movie S2: Meniscus-guided printing with aqueous Ag
catalyst ink at room temperature (AVI)
Movie S3: Tape-test to verify the adhesion of the Cu-
metallized 2D structure to the PI substrate (AVI)
Movie S4: LED sign switching using Cu grid as a
transparent conductive grid (AVI)
Movie S5: Automatic LED switch system using Cu
interconnectors on a curved substrate (AVI)
Movie S6: Extrusion-based printing of 3D grid structure
with the graphite−Ag catalyst ink (AVI)
DOI: 10.1021/acsami.8b18199
ACS Appl. Mater. Interfaces 2019, 11, 7123−7130
ACS Applied Materials & Interfaces
Movie S7: LED sign switching using 3D grid as an
electrical interconnector (AVI)
Movie S8: Operation of KERI-watch fabricated using a
custom-made hybrid 3D printing system (AVI)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: skseol@keri.re.kr. Phone: +82-55-280-1462. Fax:
+82-55-280-1590.
ORCID
Ji Tae Kim: 0000-0003-4662-0179
Seung Kwon Seol: 0000-0002-8733-4374
Author Contributions
⊥ 1989, 136, 456−462.
S.L. and M.W. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was supported by Korea Electrotechnology
Research Institute (KERI) Primary research program (19-12-
N0101-27) through the National Research Council of Science
& Technology (NST) funded by the Ministry of Science and
ICT, the Early Career Scheme (HKU 27207517) from the
Research Grants Council of Hong Kong, and the Seed Fund
for Basic Research from the University of Hong Kong
(201611159002).
■
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7130 DOI: 10.1021/acsami.8b18199

ACS Appl. Mater. Interfaces 2019, 11, 7123−7130