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Materials Chemistry C
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Air-stable, surface-oxide free Cu nanoparticles for highly

Cite this: J. Mater. Chem. C, 2013, 1,
2704
conductive Cu ink and their application to printed
graphene transistors†
Sunho Jeong,*a Su Hyeon Lee,ab Yejin Jo,a Sun Sook Lee,a Yeong-Hui Seo,a
Byeong Wan Ahn,c Gyeomuk Kim,c Gun-Eik Jang,b Jang-Ung Park,*c
Beyong-Hwan Ryua and Youngmin Choi*a

Received 21st December 2012
Accepted 13th February 2013
DOI: 10.1039/c3tc00904a
www.rsc.org/MaterialsC
Air-stable, surface-oxide free Cu nanoparticles are, for the first time, synthesized by surrounding completely
the Cu surface with oleic acid incorporated as a capping molecule. XPS analysis, in conjunction with TEM
analysis, revealed that the oleic acid is chemisorbed to the Cu surface via a chemical interaction wherein a
monodentate bond is included, without leaving behind free (non-interacting) oleic acid, thereby providing
complete surface protection against oxidation. By eliminating the surface oxide layer that critically
degrades the electrical properties, the surface-oxide free Cu nanoparticle ink facilitates the realization of
a solution-processed Cu electrode layer with resistivity as low as 4 mU cm, comparable to the resistivity
of noble metal-based, solution-processed counterparts. In addition, high resolution Cu electrode
patterns with 5 mm line-width are directly printed using an electrohydrodynamic inkjet technique, and
graphene transistors with the printed Cu electrodes demonstrate potential applications in printed
electronics.

1 Introduction been studied as candidates. Among them, the metallic nano-

Solution-processed functional materials that can be combined
with various printing techniques have recently attracted
increasing interest for use in low cost, high performance inte-
grated electronics, micro- and macro-electronics.1–5 In parti-
cular, the development of solution-processable and printable
conductor materials is of importance, as such materials have
decisive impacts on the electrical performance of various elec-
tronic devices. Accordingly, these materials should meet various
requirements including solution-processability, low-tempera-
ture processability, high conductivity, and environmental
stability.6–9 A variety of materials, such as conductive polymers,
organometallic compounds, and metallic nanoparticles, have
a
Advanced Materials Division, Korea Research Institute of Chemical Technology
(KRICT), Daejeon 305-600, Korea. E-mail: sjeong@krict.re.kr; youngmin@krict.re.kr;
Fax: +82-42-861-4151; Tel: +82-42-860-7362
b
Advanced Materials Engineering, Chungbuk National University, Cheongju 361-763,
Korea
c
School of Nano-Bioscience and Chemical Engineering, School of Mechanical and
Advanced Materials Engineering, Low-Dimensional Carbon Materials Center, Ulsan
National Institute of Science and Technology (UNIST), Ulsan 689-798, Korea.
E-mail: jangung@unist.ac.kr; Tel: +82-52-217-2533
† Electronic supplementary information (ESI) available: XPS N 1s spectrum and
thermal gravimetric analysis curves of surface-oxide free Cu nanoparticles, Cu
2p3/2 spectra of the solution-processed Cu electrode layer, top-view SEM images
of solution-processed Cu electrode layers annealed under Ar and hydrogen
atmosphere. See DOI: 10.1039/c3tc00904a
particle inks, mostly based on Ag and Au, are adequate solution-
processable materials satisfying those requirements.10–12 The
conductive polymers suffer from relatively high resistivity, and
organometallic compounds leave large amounts of organic
residues. The high cost involved in synthesizing Au, Ag nano-
particles, however, has overshadowed the advantages of this
appealing approach.
Cu nanoparticles are considered to be a viable alternative in
terms of their inexpensive chemical synthesis pathway and, in
principle, low resistivity (1.8 mU cm) comparable to that of noble
metals (Au, Ag).13–24 However, the preparation of Cu nano-
particle inks, which facilitate resistivity as low as that of Au or
Ag, has been limited owing to difficulties in synthesizing Cu
nanoparticles without a thermodynamically stable surface-
oxide layer. The presence of a surface oxide layer, even with
thickness below a few nanometers, critically degrades the
electrical properties of Cu nanoparticle-based conductive
layers.17 The preformed ultra-thin surface oxide is not reduced
completely even by annealing under a hydrogen atmosphere.
Recently, laser-induced photo-thermochemical reduction of
copper oxide was reported, but a small amount of oxide phase is
still present, resulting in a resistivity of 31 mU cm.25 Further-
more, the adoption of an oxide-free Ag surface protective layer
has not improved the electrical properties.26 To our knowledge,
even with adequate control of the surface oxidation chemistry
using various capping molecules, surface-oxide free Cu

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nanoparticle inks have not been examined so far.13–24 The
current state-of-the-art in electrical resistivity of solution-pro-
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cessed Cu conductive layers is 11 mU cm, due to the presence
of an insulating surface oxide layer.18 The inherently surface-
oxide free Au and Ag layers exhibit resistivity below 4 mU cm.
Lowering the resistivity to a level comparable to that of noble
metals is of signicant practical importance in the various
solution-processable printed electronics, since the resistance of
the conductive layer is one of the critical factors determining
the overall performance of large-area active devices. The resis-
tivity of a solution-processed Cu layer can be improved to 4 mU
cm through the elimination of the surface oxide layer, by
chemically assisted annealing using formic acid vapour.16,27,28
However, formic acid vapour is extremely reactive at elevated
temperatures, which leads to critical damage to other func-
tional layers in practical electronic devices.
In this study, we synthesize, for the rst time, surface-oxide
free Cu nanoparticles, which can be formulated readily to a
solution-processable, air-stable, highly conductive ink, via a
solvothermal synthesis method in which oleic acid is incorpo-
rated as a capping molecule. Through an in-depth X-ray
photoelectron spectroscopy (XPS) analysis, the mechanism
underlying the complete surface capping by oleic acid is
analyzed, and conductive Cu layers with resistivity below 4 mU
cm, comparable to that of noble metals, are generated without
the use of a chemically toxic atmosphere during the annealing
process. To demonstrate the suitability of this oxide-free Cu ink
for fabricating key device elements in printed electronics, we
print Cu electrode patterns with a minimum line width of 5 mm
using an electrohydrodynamic inkjet technique, and we build
working transistors employing a graphene channel and the
printed Cu source/drain electrode. Advantages in terms of low
resistivity, high-resolution printing capability, and process
simplicity in fabricating high-performance TFTs suggest the
future promise of printed electronics.
2 Experimental
2.1 Preparation of surface-oxide free Cu nanoparticle ink
All chemicals were used as received without further purica-
tion. Cu acetate (Cu(CO2CH3)2, 98%), octylamine (C8H17NH2,
99%), oleic acid (C18H34O2, 90%), phenylhydrazine
(C6H5NHNH2, 97%), and toluene (C6H5CH3, anhydrous, 99.8%)
were purchased from Aldrich. Cu nanoparticles were synthe-
sized via chemical reduction of Cu ions in octylamine under an
inert atmosphere. To prevent interparticular agglomeration and
surface oxidation, oleic acid was incorporated as a surface
capping molecule and phenylhydrazine was used as a reducing
agent. 10.4 g of Cu acetate and 25.1 g of oleic acid were added
into a three-neck round-bottomed ask containing 73.6 mL of
octylamine. The ask was tted with a reux condenser and a
mechanical stirrer. The solution was purged with nitrogen for
60 min and then heated to 150  C. Then, phenylhydrazine was
added dropwise and the reaction was continued for 120 min.
Aer the completion of synthesis reaction, the synthesized Cu
nanoparticles were separated by centrifugation and washed
with toluene. The synthesized Cu nanoparticles were kept in air
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Journal of Materials Chemistry C
without additional surface-passivation procedures. For the
preparation of the Cu conductive ink, the obtained Cu nano-
particles were dispersed in toluene. The solid loading was 30 wt
%. Then, the prepared inks were subjected to ball milling for
1 h. By casting the prepared Cu conductive ink, the conductive
Cu electrode layer was prepared on a glass substrate. The cast
Cu nanoparticulate lms were dried at 80  C in a vacuum oven
and annealed at various temperatures from 150 to 300  C for
120 min under either an Ar or a hydrogen (10%) atmosphere.
2.2 Electrohydrodynamic inkjet printing
For making a nozzle for electrohydrodynamic inkjet printing, Cr
(thickness: 10 nm)/Cu (70 nm)/Au (20 nm) layers were succes-
sively evaporated onto the outer surface of glass pipettes with
tip internal diameters of 5 and 10 mm (World Precision Instru-
ments). By dipping the tip of the metal-coated pipette into
1H,1H,2H,2H-peruorodecane-1-thiol solution (0.01 wt% in
dimethylformamide) for 30 min, a hydrophobic self-assembled
layer was formed on the gold surface of the pipette tip.
Suspensions of oxide-free Cu nanoparticles in dipropylene
glycol propyl ether with a concentration of 4 wt% were used as
the ink for electrohydrodynamic inkjet printing. The capillary
nozzle was connected to a chamber, and a syringe pump
delivered the ink from the chamber to the nozzle tip, to form a
pendant ink meniscus. The metal-coated nozzle served as an
electrode to apply an electric eld. The substrate was positioned
on an electrically conducting plate, and a conducting support
for the substrate was grounded while the nozzle was biased for
printing.44,48 The distance between the nozzle and the substrate
was 100 mm.
2.3 Fabrication of graphene-TFTs employing printed Cu
electrodes
Aer loading a Cu foil (Alfa Aesar, item no. 13382) onto the
center of a quartz CVD chamber under vacuum (100 mTorr), the
furnace was heated up to 1000  C under the ow of Ar (200
sccm) and H2 (500 sccm). CVD growth was carried out under the
ow of CH4 (12 sccm) and H2 (500 sccm) for 5 minutes, and then
the chamber was cooled to room temperature under the ow of
Ar (500 sccm) over ca. 30 min. A 200 nm thick poly(methyl
methacrylate) (MicroChem Corp. 950 PMMA) supporting layer
was spun on the synthesized graphene sample. The foil was
dissolved in a diluted etching solution of FeCl3 : HCl : H2O
(1 : 1 : 20 vol%), allowing the PMMA-coated graphene layer to
oat on the solution surface. Subsequently, the sample was
transferred onto a n+-Si wafer with a 300 nm thick SiO2 surface,
and the PMMA supporting layer was removed using acetone.
Aer isolating graphene channel areas with O2 plasma, the Cu
nanoparticle ink was printed for forming source and drain
electrodes, followed by annealing at 300  C under a hydrogen
(10%) atmosphere.
2.4 Measurements
The size and shape of synthesized Cu nanoparticles, and the
microstructures of Cu electrode layers annealed at different
temperatures were observed by transmission electron
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microscopy (TEM, JEM-4010, JEOL) and scanning electron
microscopy (SEM, JSM-6700, JEOL). The crystal structure of Cu
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nanoparticles was analyzed using an X-ray diffractometer (XRD,
D/MAX-2200V, Rigaku) and chemical structural analyses of Cu
nanoparticles and printed Cu patterns were performed by X-ray
photoelectron spectroscopy (XPS, K-Alpha, Thermo Fisher
Scientic). The thermal behavior of Cu nanoparticles was
monitored using thermal gravimetric analysis (SDT2960, TA
Instruments) at a heating rate of 5  C min 1. The resistivity of
the Cu conductive layers was analyzed with a four point probe
station equipped with a semiconductor characterization system
(Keithley 4200, Keithley). The proles of the printed Cu patterns
were scanned using an atomic force microscope (Dimension
3100, Veeco), and the Raman spectrum of graphene was
obtained at 532 nm wavelength using a Raman microscope
(alpha 300S, Witec). Transfer characteristics of TFTs were
measured with the probe station with the semiconductor
analyzer. The viscosity, surface tension and contact angle of
prepared Cu inks were measured using a rheometer (Physica
MCR 101, Anton Paar), surface tension analyzer (New DST,
SEO), and dynamic contact angle system (SEO 300, SEO),
respectively.
3 Results and discussion
The surface-oxide free Cu nanoparticles were synthesized via
chemical reduction of Cu ions in octylamine under an inert
atmosphere. The resulting Cu nanoparticles were stable in air
without further surface passivation. As shown in Fig. 1a, the
average particle size of Cu nanoparticles, with a bimodal
particle size distribution, is 42.3 and 108.3 nm. The structural
requirement for a well-interconnected particulate network is a
high packing density for increasing the interparticular junction
area where mass transport takes place.29 For metal nano-
particles with a bimodal particle size distribution, the small
Fig. 1 (a) SEM image, (b) XRD result, (c) low-magnification TEM image, and (d)
high-magnification TEM image of surface-oxide free Cu nanoparticles. The arrows
in the TEM image indicate the surface shell layer.
2706 | J. Mater. Chem. C, 2013, 1, 2704–2710
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nanoparticles are placed in voids between neighboring large
particles, which leads to a well-packed particulate structure as
well as a low-temperature densication reaction.30 The size of
tetrahedral interstices, which form between ideally packed
108.3 nm-sized particles, is 44.8 nm, corresponding closely to
the average particle size of small Cu nanoparticles. According to
the XRD analysis, the synthesized Cu nanoparticles consisted of
a pure Cu phase without oxide phases (CuO, Cu2O) or secondary
phases (Fig. 1b). However, since the surface oxide layer is
amorphous and the volume of the surface oxide layer is quite
small, XRD analysis is not suitable for analysing precisely the
presence of the surface oxide layer. TEM analysis, which can be
employed to visualize the nanoscale surface structure, offers
more accurate information on the surface oxide layer. In the
TEM image, the nanoparticle assembly, in which the small
nanoparticles are placed between large nanoparticles, was
observed (Fig. 1c). It was also revealed that the crystalline Cu
core is surrounded by the amorphous shell layer with a thick-
ness of 1 nm (Fig. 1d), which might be composed of capping
molecules and the surface oxide layer. To date, it has been
reported that Cu nanoparticles synthesized via a wet chemical
synthetic method are inevitably composed of a thin shell layer
with a thickness of 2–4 nm,13,17,18,24 which has been recognized
as a critical drawback in improving the conductivity. Judging
from the thickness of the amorphous shell layer, it is tentatively
presumed that the Cu nanoparticles synthesized in this study
possess a far thinner surface oxide layer.
In order to obtain in-depth information on the presence of a
surface oxide layer and the capping mechanism of oleic acid, an
XPS analysis was carried out. In the XPS spectrum of Cu 2p3/2,
the symmetric peak at 932.6 eV is assigned to Cu and other
peaks due to either Cu2O or CuO are absent, indicative of the
Fig. 2 XPS (a) Cu 2p3/2, (b) C 1s, and (c) O 1s spectra of surface-oxide free Cu
nanoparticles. (d) Schematic diagram showing the structures of extended
conformations of oleic acid in monodentate and bidentate bonds.
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absence of a surface oxide layer (Fig. 2a); thus, it is believed that
the amorphous shell layer is predominantly composed of oleic
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acid capping molecules. The absence of the N 1s peak implies
the preferred adsorption of oleic acid over octylamine on the Cu
nanoparticle surface (Fig. S1 in ESI†). In order to analyze how
the oleic acid surrounds effectively the Cu core without leaving a
surface oxide layer, the C 1s and O 1s peaks were investigated.
As shown in Fig. 2b, the C 1s peaks at 284.5 and 288.4 eV are
ascribed to the alkyl chain (C–C) and the carboxylate (–COO )
moiety, respectively.31–33 The tted Gaussians give an integrated
area ratio of 1 : 16.7, in good agreement with the molecular
stoichiometry of oleic acid. In addition, no peak corresponding
to carboxylic carbon appeared in the spectrum, indicating that
all of the oleic acids present on the Cu nanoparticles are
interacted chemically with Cu atoms. The absence of free
capping molecules would allow a densely packed protective
layer to be formed.17 Regarding the O 1s peak, the asymmetric O
1s peak reveals the presence of oxygen atoms with different
chemical surroundings in the carboxylate moiety (Fig. 2c). The
O 1s peaks positioned at 530.4 and 531.8 eV are assigned to
oxygen atoms in C–O and C]O, respectively. It could be con-
jectured that the peak due to the carbonyl group originates from
free oleic acids. However, since the absence of free oleic acid
was conrmed by the analysis of the C 1s spectrum, it is
determined that the C]O results from the carboxylate moiety.
When carboxylic acids adsorb from the solution to the metal
surface, there are two bonding types of carboxylate groups:
monodentate bonding through inequivalent oxygen atoms
(C–O, C]O) with molecular stoichiometry of 1 : 1, and biden-
tate bonding with two equivalent oxygen atoms (C–O),34,35 as
depicted in Fig. 2d. According to an integrated area analysis, the
ratio of the monodentate to bidentate bond is 1.66, which
implies that the predominant bond is monodentate. Note that
both bonds are present for the surface oxide-free Cu nano-
particles synthesized in this study, whereas for other metal
surfaces, the carboxylic acid mainly interacts via bidentate
bonding.33,36,37 The monodentate bond, where only one O atom
interacts directly with the metal surface, enables carboxylic acid
molecules to be tilted asymmetrically from the surface, yielding
higher surface coverage.33 It is thus postulated that the surface-
oxide free Cu nanoparticles were achieved by the formation of a
metal surface capped completely by oleic acid via mixed
chemical interactions including monodentate bonding with
higher surface coverage.
For the fabrication of solution-processed Cu conductive
layers, the synthesized Cu nanoparticles were dispersed in
toluene with a particle content of 30 wt%. The viscosity, surface
tension, and contact angle on a glass substrate were measured
to be 5.6 cP, 26.5 mN m 1, and 5 , respectively. The prepared Cu
ink was deposited on a glass substrate, dried at 80  C, and
annealed at temperatures ranging from 150 to 350  C. Under an
Ar atmosphere, the resistivity was measured to be 3  107, 164,
5.9, and 5.5 mU cm at 200, 250, 300 and 350  C, respectively
(Fig. 3a). As shown in Fig. S2 in ESI,† under an inert atmo-
sphere, the thermal decomposition of oleic acid starts above
200  C and is complete at 350  C, indicating that the resistivity
should be improved gradually within this temperature range.
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Journal of Materials Chemistry C
Fig. 3 (a) Resistivity evolution of solution-processed conductive Cu layers as a
function of annealing temperature under either an Ar or a hydrogen (10%)
atmosphere; (b) SEM image of Cu layers annealed at either 200 or 250  C under
either an Ar or a hydrogen atmosphere. The scale bar in SEM images is 200 nm.
The capping molecules surrounding metal nanoparticles
hinder mass transport for densication between neighboring
nanoparticles. With regard to effective removal during the
annealing process, capping molecules with a short chain length
weakly bound to the metal surface are favorable. However, such
capping molecules are not acceptable for Cu nanoparticles,
since they are not capable of forming a densely packed,
complete surface protection layer. The organic moiety with a
long chain length should be strongly chemisorbed to the meal
surface as capping molecules. In order to get rid of the organic
capping molecules, two-step annealing (in air and subsequently
under a hydrogen atmosphere) can be adopted in a sophisti-
cated controlled manner. However, the surface oxide, undesir-
ably formed during the annealing in air, is not completely
reduced by annealing under a hydrogen atmosphere, yielding
resistive Cu layers.38
However, oleic acid chemisorbed to the metal surface can be
easily transformed to a volatile moiety, oleyl alcohol, resulting
in the O–C bond rupture, when a small amount of hydrogen is
supplied at a relatively low temperature.39 The O–C bond
rupture was conrmed by the compositional analysis based on
XPS spectra of Cu lms annealed at different temperatures
under either an inert or a hydrogen atmosphere. As shown in
Fig. S3 in the ESI,† for Cu lms thermally treated under a
hydrogen atmosphere, the reduction of oxygen content was
clearly observed, indicative of facile removal of capping mole-
cules. The resistivity was measured to be 21, 3.9, 3.5, and 3.4 mU
cm aer annealing at 200, 250, 300, and 350  C, respectively,
under a mild hydrogen (10%) atmosphere. Compared with the
resistivity of the Cu layers annealed under an Ar atmosphere,
the resistivity was improved drastically by a factor of 1.4  106 at
200  C and 42 at 250  C, in a temperature range at which the
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capping molecules are not entirely decomposed under an Ar
atmosphere. For the Cu conductive layer annealed under a
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hydrogen atmosphere, the distinct microstructural evolution
into a uniformly interconnected, conductive particulate layer
was observed, as revealed by SEM images (Fig. 3b). In the case of
annealing under an Ar atmosphere, isolated individual Cu
nanoparticles persisted. According to XPS analysis results for
Cu layers annealed at different temperatures (Fig. S4 in ESI†),
further surface oxidation did not occur during annealing under
both Ar and hydrogen atmosphere; thus, it is believed that the
different dependency of resistivity on annealing temperature is
predominantly associated with the microstructural densica-
tion involved with the thermally/chemically activated
decomposition of capping molecules. The different tempera-
ture-dependent densication behaviours at overall annealing
temperatures are shown in Fig. S5 and S6 in ESI.† Note that
resistivity below 4 mU cm is comparable to that of conductive
layers derived from Ag nanoparticles with carboxyl acid-termi-
nated capping molecules7,9,40–43 (unlike Cu layers, Ag layers were
annealed in air, which is benecial in terms of the thermal
decomposition of capping molecules). This achievement has
been facilitated based on well-controlled surface chemistry for
synthesizing surface-oxide free Cu nanoparticles and the easy
removal of densely packed capping molecules. This implies that
oleic acid is a capping molecule that essentially enables the
realization of high performance, solution-processable Cu
nanoparticles. To date, in several reports including our recent
work, oleic acid has been adopted as a capping molecule for Cu
nanoparticles.18,22–24 However, the highly conductive, surface-
oxide free Cu nanoparticles have not been demonstrated due to
the lack of in-depth studies on surface capping and straight-
forward formation of a volatile moiety. Unlike other method-
ologies, our well-designed synthetic method is based on the use
of phenylhydrazine as a reducing agent, octylamine as a solvent,
and oleic acid as a capping agent. The chemically interacting
chemical moieties, such as octylamine and oleic acid, are
essential to stabilize the Cu ions prior to nucleation and growth,
preventing the surface oxidation. Also, the incorporation of a
mild reducing agent, phenylhydrazine, enables the controllable
surface oxidation chemistry. Therefore, it is believed that the
combinatorial synthetic pathway using phenylhydrazine, octyl-
amine, and oleic acid endowed an opportunity to synthesize the
surface oxide-free Cu nanoparticles. In fact, the incorporation of
hydrazine as a reducing agent or toluene as a solvent did not
allow for the formation of surface oxide-free Cu nanoparticles
with the synthetic batch composition tested in this study.
The long-term stability of prepared Cu inks was investigated
by monitoring the resistivity variation of Cu lms prepared
using Cu nanoparticles stored in ink for different timeframes
up to 2 months in dry air. The resistivity variation reects the
long-term anti-oxidation stability of Cu nanoparticles in ink,
since the dispersion stability was maintained well even over 2
months, which was conrmed by the sedimentation test and UV
absorption test. As shown in Fig. S7 in the ESI,† the resistivity
did not vary up to 7 weeks, indicative of complete surface
passivation for a prolonged time even in air. The slightly
increased resistivity over 8 weeks might be attributable to the
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Fig. 4 Electrohydrodynamic inkjet printing of Cu electrodes. (a) Optical micro-
graph and (b) AFM image and depth profile of the 13 mm wide Cu electrode; (c)
optical micrograph and (d) AFM image and depth profile of the 5 mm wide Cu
electrode. Scale bar in (a) and (c) is 100 and 10 mm, respectively.
subtle surface oxidation, but the resistivity is still comparable to
that of as-prepared Cu lms reported elsewhere.13–24
Printed electronics represents an important application area
that can take advantage of the highly conductive nanoparticles.
For demonstrating their compatibility with nozzle-based, direct
printing techniques, we patterned multiple Cu electrode lines
with different widths using an electrohydrodynamic inkjet
technique.44 Compared with commercially available thermal/
piezoelectric inkjet systems that have coarse printing resolu-
tions due to limitation in the droplet ejection with decreasing
nozzle size,45,46 electrohydrodynamic inkjet (e-jet) printing
exploits electric elds to eject jets or droplets of inks, allowing
the much narrower patterned-structures.47 The simplicity of e-
jet printing, with which the electrostatic force can be increased
by applying higher electric elds, facilitates the use of smaller
nozzles, which are important to achieve higher resolution.44,47,48
Fig. 4a and b present an optical micrograph and an AFM image
of the Cu electrode lines, with a width of 13 mm, printed onto a
n+-Si wafer with a 300 nm thick SiO2 top layer. For the results,
the Cu nanoparticle ink was printed using a 10 mm internal-
diameter nozzle at a printing speed of 5 mm s 1, and the Cu
pattern was annealed at 300  C in Ar with 10% H2 aer printing.
The printing resolution can be improved further by using
smaller nozzles. For example, a line width of 5 mm can be
achieved with a 5 mm internal-diameter nozzle, as shown in
Fig. 4c and d. This high resolution exceeds that of conventional
thermal/piezoelectric inkjet systems, the narrowest printable
lines of which are 30 mm in width.
As a demonstration of device fabrication using the Cu ink,
thin-lm transistors (TFTs), which employ graphene as a
channel layer and the e-jet printed Cu patterns as a source/drain
electrode, were fabricated on a n+-Si wafer (bottom gate) with a
300 nm thick SiO2 dielectric layer. Graphene has been explored
as a two-dimensional (2D) nanomaterial with high carrier
mobility, mechanical exibility, optical transparency, and
thermal conductivity, and has demonstrated simple device
functions based on mostly conventional lithography
processes.49–51 The approaches to adopt this high-performance
2D material in printed electronics are important for low-cost,
next-generation electronics. Fig. 5a illustrates a schematic
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Fig. 5 (a) Schematic illustration of the transistor layout, where the source/drain
electrodes are printed by e-jet, (b) Raman spectrum from the graphene channel,
and (c) ID–VG characteristic of the graphene TFT (channel length and width: 60 
60 mm, VD: 30 mV).
diagram of the device layouts, and Fig. 5b shows a typical
Raman spectrum obtained from the graphene channel, exhib-
iting three characteristic bands of graphene (D: centred at
1350 cm 1, G: centred at 1590 cm 1, 2D: centred at
2680 cm 1).49 This spectrum presents (i) the G-to-2D peak
intensity ratio of 0.5, (ii) the FWHM value of 30 cm 1 for the
2D band, and (iii) the D-to-G peak intensity ratio below 0.1,
which indicates a monolayer graphene sheet with a relatively
low defect density.49 Source/drain current (ID) versus back-gate
bias (VG) characterization of the TFT was measured at room
temperature in air (Fig. 5c). This graph shows ambipolar
behavior consistent with the expected semimetallic character-
istics of graphene,50–52 with a positive charge neutrality point of
13 V. The graphene transistor with the e-jet printed Cu elec-
trodes showed a hole (electron) mobility of 1280 (660) cm2 V 1
s 1, calculated using a standard metal–oxide–semiconductor
TFT model.
4 Conclusions
In summary, we synthesized, for the rst time, surface-oxide
free Cu nanoparticles via a solvothermal method in which oleic
acid is incorporated as a capping molecule. According to XRD,
TEM, and XPS analyses, it was revealed that the shell layer, with
a thickness of 1 nm, is only composed of oleic acid. The oleic
acid interacts with the Cu surface via a monodentate bond as
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Journal of Materials Chemistry C
well as a bidentate bond, completely preventing surface oxida-
tion. By resolving two critical drawbacks, (i) the presence of a
thermodynamically stable surface oxide and (ii) the difficulty in
removing the organic capping molecules, the solution-pro-
cessed, highly conductive Cu layers with resistivity below 4 mU
cm were demonstrated. High-resolution patterns of the Cu
electrodes, printed directly using an electrohydrodynamic ink-
jet technique, and the resulting functional graphene transistors
suggest the future promise of printed electronics. We expect
that this chemical methodology can be extended to various
oxidizable metal nanoparticle (including Ni, Al, and Co)-based
electronic applications, which have not been heretofore fullled
successfully due to the difficulty in suppressing the formation
of the surface oxide layer.
Acknowledgements
This study was supported by the Industrial Core Technology
Development Program funded by the Ministry of Knowledge
Economy (no. 10031709, Development of Direct Nanopatterning
Technology for Electronic Devices). This research has been also
performed as KRICT's own project and supported by the Korea
Research Institute of Chemical Technology (KRICT). J.-U. P.
thanks the National Research Foundation of Korea
(20110014111).
Notes and references
1 H. J. Park, M.-G. Kang, S. H. Ahn and L. J. Guo, Adv. Mater.,
2010, 22, E247.
2 K.-Y. Chun, Y. Oh, J. Rho, J.-H. Ahn, Y.-J. Kim, H. R. Choi and
S. Baik, Nat. Nanotechnol., 2010, 5, 853.
3 S. Jeong, Y.-G. Ha, J. Moon, A. Facchetti and T. J. Marks, Adv.
Mater., 2010, 22, 1346.
4 E. Menard, M. Meitl, Y. Sun, J.-U. Park, D. Shir, Y.-S. Nam,
S. Jeon and J. A. Rogers, Chem. Rev., 2007, 107, 1117.
5 S. Jeong and J. Moon, J. Mater. Chem., 2012, 22, 1243.
6 M. Grouchko, A. Kamyshny, C. F. Mihailescu, D. F. Anghel
and S. Magdassi, ACS Nano, 2011, 5, 3354.
7 S. Jeong, H. C. Song, W. W. Lee, Y. Choi, S. S. Lee and
B.-H. Ryu, J. Phys. Chem. C, 2010, 114, 22277.
8 S. Magdassi, M. Grouchko and A. Kamyshny, ACS Nano,
2010, 4, 1943.
9 S. Jeong, H. C. Song, W. W. Lee, Y. Choi and B.-H. Ryu, J.
Appl. Phys., 2010, 108, 102805.
10 Y. Wu, Y. Li and B. S. Ong, J. Am. Chem. Soc., 2007, 129, 1862.
11 D. Kim, S. Jeong, H. Shin, Y. Xia and J. Moon, Adv. Mater.,
2008, 20, 3084.
12 Q. J. Cai, M. B. Chan-Park, Z. S. Lu, C. M. Li and B. S. Ong,
Langmuir, 2008, 24, 11889.
13 B. K. Park, S. Jeong, D. Kim, J. Moon, S. Lim and J. S. Kim, J.
Colloid Interface Sci., 2007, 311, 417.
14 P. Christian and M. Bromeld, J. Mater. Chem., 2010, 20,
1135.
15 H.-T. Zhu, Y.-S. Lin and Y.-S. Yin, J. Colloid Interface Sci.,
2004, 277, 100.
J. Mater. Chem. C, 2013, 1, 2704–2710 | 2709

Journal of Materials Chemistry C
16 Y. Lee, J.-R. Choi, K. J. Lee, N. E. Stott and D. Kim,
Nanotechnology, 2008, 19, 415604.
Published on 13 February 2013. Downloaded by Central Mechanical Engineering Research Institute (CSIR) on 4/5/2019 4:45:11 AM.
17 S. Jeong, K. Woo, D. Kim, S. Lim, J. S. Kim, H. Shin, Y. Xia
and J. Moon, Adv. Funct. Mater., 2008, 18, 679.
18 S. Jeong, H. C. Song, W. W. Lee, S. S. Lee, Y. Choi, W. Son,
E. D. Kim, C. H. Paik, S. H. Oh and B.-H. Ryu, Langmuir,
2011, 27, 3144.
19 C. Salzemann, L. Lisiecki, J. Urban and M. P. Pileni,
Langmuir, 2004, 20, 11772.
20 S. H. Wu and D. H. Chen, J. Colloid Interface Sci., 2004, 273, 165.
21 Y. H. Wang, P. L. Chen and M. H. Liu, Nanotechnology, 2006,
17, 6000.
22 D. Mott, J. Galkowski, L. Y. Wang, J. Luo and C. J. Zhong,
Langmuir, 2007, 23, 5740.
23 P. Kanninen, C. Johans, J. Merta and K. Kontturi, J. Colloid
Interface Sci., 2008, 318, 88.
24 S. Jeong, H. C. Song, W. W. Lee, H. J. Suk, S. S. Lee, T. Ahn,
J.-W. Ka, Y. Choi, M. H. Yi and B.-H. Ryu, J. Mater. Chem.,
2011, 21, 10619.
25 B. Kang, S. Ham, J. Kim, S. Ko and M. Yang, J. Phys. Chem. C,
2011, 115, 23664.
26 M. Grouchko, A. Kamyshny and S. Magdassi, J. Mater. Chem.,
2009, 19, 3057.
27 K. Woo, Y. Kim, B. Lee, J. Kim and J. Moon, ACS Appl. Mater.
Interfaces, 2011, 3, 2377.
28 I. Kim and J. Kim, J. Appl. Phys., 2010, 108, 102807.
29 M. N. Rahaman, in Ceramic Processing, CRC Press, Boca
Raton, FL, 2007.
30 K. Woo, D. Kim, J. S. Kim, S. Lim and J. Moon, Langmuir,
2009, 25, 429.
31 V. V. Korolev, A. G. Ramzanova and A. V. Blinov, Russ. Chem.
Bull., 2002, 51, 2044.
32 E. Frydman, H. Cohen, R. Maoz and J. Sagiv, Langmuir, 1997,
12, 55089.
33 N. Wu, L. Fu, M. Su, M. Aslam, K. C. Wong and V. P. Dravid,
Nano Lett., 2004, 4, 383.
34 L. H. Dubois, B. R. Zegarski and R. G. Nuzzo, Langmuir, 1986,
2, 412.
2710 | J. Mater. Chem. C, 2013, 1, 2704–2710
View Article Online
Paper
35 M. Wühn, J. Weckesser and C. Woll, Langmuir, 2001, 17,
7605.
36 R. J. Jouet, A. D. Warren, D. M. Rosenberg, V. J. Bellitto,
K. Park and M. R. Zachariah, Chem. Mater., 2005, 17, 2987.
37 L. Zhang, R. He and H.-C. Cu, Appl. Surf. Sci., 2006, 253, 2611.
38 A. Yabuki and N. Arriffin, Thin Solid Films, 2010, 518, 7033.
39 W. K. Lewis, A. T. Rosenberger, J. R. Gord, C. A. Crouse,
B. A. Harruff, K. A. Shiral Fernando, M. J. Smith,
D. K. Phelps, J. E. Spowart, E. A. Guliants and
C. E. Bunker, J. Phys. Chem. C, 2010, 114, 6377.
40 S. Magdassi, M. Grouchko, O. Berezin and A. Kamyshny, ACS
Nano, 2010, 4, 1943.
41 Y. Wu, Y. Li and B. S. Ong, J. Am. Chem. Soc., 2007, 129, 1862.
42 M. Grouchko, A. Kamyshny, C. F. Mihailescu, D. F. Anghel
and S. Magdassi, ACS Nano, 2011, 5, 3354.
43 Y. Wu, Y. Li and B. S. Ong, J. Am. Chem. Soc., 2006, 128, 4202.
44 J.-U. Park, M. Hardy, S. J. Kang, K. Barton, K. Adair,
D. K. Mukhopadhyay, C. Y. Lee, M. S. Strano, A. G. Alleyne,
J. G. Georgiadis, P. M. Ferreira and J. A. Rogers, Nat.
Mater., 2007, 6, 782.
45 Y. Wang and J. Bokor, J. Micro/Nanolithogr., MEMS, MOEMS,
2007, 6, 043009.
46 J. Stringer and B. Derby, J. Eur. Ceram. Soc., 2009, 29, 913.
47 H. K. Choi, J.-U. Park, O. O. Park, P. M. Ferreira,
J. G. Georgiadis and J. A. Rogers, Appl. Phys. Lett., 2008, 92,
123109.
48 J.-U. Park, S. Lee, S. Unarunotai, Y. Sun, S. Dunham, T. Song,
P. M. Ferreira, A. G. Alleyene, U. Paik and J. A. Rogers, Nano
Lett., 2010, 10, 584.
49 M. S. Dresselhaus, A. Jorio, M. Hofmann, G. Dresselhaus and
R. Saito, Nano Lett., 2010, 10, 751.
50 X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner,
A. Velamakanni, I. Jung, E. Tutuc, S. K. Banerjee,
L. Colombo and R. S. Ruoff, Science, 2009, 324, 1312.
51 C. Mattevi, H. Kim and M. A. Chowalla, J. Mater. Chem., 2011,
21, 3324.
52 J.-U. Park, S. Nam, M. S. Lee and C. M. Lieber, Nat. Mater.,
2012, 11, 120.
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