Article

www.acsnano.org

High-Resolution Transfer Printing of Graphene

Lines for Fully Printed, Flexible Electronics
Donghoon Song, Ankit Mahajan, Ethan B. Secor, Mark C. Hersam, Lorraine F. Francis,
and C. Daniel Frisbie*,

Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, United States

Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, United
States
*
S Supporting Information

ABSTRACT: Pristine graphene inks show great promise for

exible printed electronics due to their high electrical
conductivity and robust mechanical, chemical, and environ-
mental stability. While traditional liquid-phase printing
methods can produce graphene patterns with a resolution of
30 m, more precise techniques are required for improved
device performance and integration density. A high-
resolution transfer printing method is developed here
capable of printing conductive graphene patterns on plastic
with line width and spacing as small as 3.2 and 1 m,
respectively. The core of this method lies in the design of a
graphene ink and its integration with a thermally robust mold that enables annealing at up to 250 C for precise, high-
performance graphene patterns. These patterns exhibit excellent electrical and mechanical properties, enabling favorable
operation as electrodes in fully printed electrolyte-gated transistors and inverters with stable performance even following
cyclic bending to a strain of 1%. The high resolution coupled with excellent control over the line edge roughness to below
25 nm enables aggressive scaling of transistor dimensions, oering a compelling route for the scalable manufacturing of
exible nanoelectronic devices.
KEYWORDS: pristine graphene ink, hydrophobic molds, transfer printing, high-resolution graphene patterns, exible electronics

H igh-resolution printing of electronically functional

inks on plastic or paper substrates is a compelling
manufacturing platform for large-area, low-cost,
exible electronic systems with applications in sensors, displays,
energy devices, smart packaging, and radio frequency
identication.113 A cornerstone of this technology is the
design and integration of functional liquid inks and reliable,
high-resolution patterning methods. Among emerging nano-
material inks, graphene oers a suite of desirable properties for
printed electronics, including high electrical conductivity,
exibility, and robust mechanical, chemical, and environmental
stability.14,15 Graphene can be produced in a scalable manner
by liquid-phase exfoliation, using methods such as ultra-
sonication,16 high-shear mixing,17 microuidization,18 and
other techniques.1923 Proper engineering of the uid proper-
ties, including solvent composition and dispersants or additives,
enables the integration of graphene with a variety of printing
methods.2430 Moreover, these methods can in many cases be
translated to additional nanomaterials, enabling the straightfor-
ward fabrication of heterostructures.3133 One class of
graphene inks, containing exfoliated graphene akes stabilized
by ethyl cellulose in organic solvent, has shown signicant
promise for versatile process integration while maintaining
excellent performance metrics.3437 In particular, the tunable
ink rheology of these pristine graphene inks oers compatibility
with various printing methods such as inkjet, gravure, and
screen printing. The resulting graphene patterns oer electrical
conductivity as high as 25,000 S/m and excellent tolerance to
extreme bending stresses even for thick lms (>1 m), enabling
bendable and foldable printed organic transistors.3437 More-
over, this platform for ink development is cost-eective and
scalable, with established relevance for commercial distribution.
However, the demonstrated printing resolution for pristine
graphene inks has to-date been limited to 30 m,3437 primarily
due to lateral spreading of the functional inks which results in
low aspect ratio features with suboptimal conductance. In
addition, line edge roughness decreases print consistency and
yield for high-resolution, closely spaced features such as
transistor electrodes. As such, a reliable route to printed
graphene patterns with line width and spacing of several
Received: May 30, 2017
Accepted: July 7, 2017
Published: July 7, 2017

XXXX American Chemical Society A DOI: 10.1021/acsnano.7b03795

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Figure 1. (a,b) Schematics of graphene ink showing graphene sheets stabilized by ethyl cellulose. (c) Shear viscosity of the graphene ink
measured at room temperature, 150 mPas at a shear rate of 0.1 s1 (inset: photograph of graphene ink). (d) Representative AFM image of
graphene akes. Distribution of (e) ake thickness and (f) ake area for >500 akes.
microns is highly desirable for the development of high-
performance exible electronic devices.
Transfer printing, a rapid method for transferring patterns
from a patterned template or mold to a receiving substrate,38
oers suitable prospects for achieving high-resolution pattern-
ing of electronic materials such as graphene.20 Compared to
other very high-resolution printing methods, such as electro-
hydrodynamic jet printing,39 it is more straightforward for
patterning thick features necessary for high conductance.
However, only thin graphene lms (<100 nm in thickness)
have been favorably transfer printed.40,41 In this regard,
graphene inks based on cellulosic polymers are a compelling
option for achieving graphene patterns with high resolution,
conductivity, and thicknesses >1 m.36 To integrate this
graphene ink with transfer printing on exible substrates,
thermal annealing requirements of the inks must be addressed.
In principle, transfer printing oers the opportunity to decouple
thermal annealing processes of inks with the thermal tolerance
of the receiving substrate, in that annealing can be performed in
a suitable mold prior to transfer to the substrate. However, the
development of a thermally stable mold with precise, high-
resolution features and properly engineered wetting properties
presents a challenge in this regard.
Herein, we demonstrate a high-resolution transfer printing
method for graphene inks based on selective dewetting42,43
using robust silicon molds with an engineered low surface free
energy (). Low viscosity (500 mPas) of graphene inks for
successful transfer printing is essential. High-viscosity (>1000
mPas) graphene ink is not desired because such inks exhibit
limited spreading on the mold. The high thermal stability of the
mold allows annealing of the low-viscosity graphene inks prior
to transfer at temperatures as high as 250 C. This feature
enables broad process compatibility by decoupling the thermal
annealing requirement of printed materials from the thermal
tolerance of the receiving substrate and marks a clear
distinction from conventional transfer printing methods, in
which annealing of high-performance materials is completed on
the nal substrate after transfer. Furthermore, the molds can be
exible and are thus well-suited to roll-to-roll processing
(Figure S1, Supporting Information). Upon transfer printing,
high-resolution conductive graphene patterns featuring a
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smooth surface and clean edges are obtained; notably, line
width and spacing as small as 3.2 and 2.7 m, respectively, were
realized, with line edge roughness smaller than 25 nm. To the
best of our knowledge, this is the highest resolution reported to
date for printed graphene features. The excellent electrical and
bending performance of these graphene electrodes are
leveraged in electrolyte-gated transistors (EGTs)35,36,4446
fabricated with correspondingly high mechanical robustness
and demonstrating the great potential of this strategy for
exible electronics applications.
RESULTS AND DISCUSSION
The graphene ink for transfer printing contains graphene sheets
that are well exfoliated and stabilized by the polymer stabilizer
ethyl cellulose in a solvent mixture composed of terpineol and
cyclohexanone (Figure 1a,b). Briey, for the ink fomulation, a
desired solid powder comprising graphene akes and excess
ethyl cellulose (2:3, w/w) was rst produced by liquid-phase
exfoliation and occulation methods.35 Graphene ink was then
produced with 20% w/v solids in terpineol, exhibiting a shear
viscosity of 1000 mPas at a shear rate 0.1 s1 (Figure S2).
Owing to the direct dispersion of pristine graphene akes
exfoliated from natural graphite and the favorable eects of the
polymer, excellent electrical properties are typical.3437 A low
viscosity 500 mPas is required for selective dewetting and
mold lling,43 and thus, the as-prepared ink was diluted using
50% cyclohexanone, a preferred solvent for viscosity control of
graphene inks.37 The desirable viscosity 150 mPas was
yielded as shown in Figure 1c. This low-viscosity ink assures
stable performance even after a year or more, using as necessary
a facile redispersion under ultrasonic bath for about 10 min.
Such stability is notable because the ink was prepared directly
from natural graphite without damaging, oxidizing treatments
typically used to ensure adequate dispersion. The graphene
akes used in the ink have a nanoscale dimension, typical
thickness of 2 nm and lateral area of 65 65 nm as
determined by atomic force mircoscopy (AFM) (Figure 1df),
a desirable size for high-resolution printing.
A schematic illustration of the high-resolution transfer
printing process is depicted in Figures 2 and 3. First, a silicon
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Figure 2. (a) Schematics for selective dewetting and annealing of graphene ink on the Cytop/Si mold. The trench depth is 3 m. (b) SEM
images of ve groups of graphene lines in the mold, separated by 40 m. Each group has three single lines, with dierent spacings of 2.7, 5.7,
8.7, 11.7, and 14.7 m, from left to right. (c) Corresponding 3D images (not to scale). (d) Enlarged SEM images of graphene lines spaced by
2.7 m.

Figure 3. (a) Schematic illustration showing pattern transfer of high-resolution graphene lines to PET, using the UV-curable NOA73 adhesive.
(b) SEM images of ve groups of transferred graphene lines on the PET, separated by 40 m. Each group has three single lines, with dierent
spacing of 2.7, 5.7, 8.7, 11.7, and 14.7 m, from left to right. (c) Corresponding 3D images (not to scale). (d) Enlarged SEM images of printed
graphene lines spaced by 2.7 m.

wafer (Si) was patterned by conventional microlithography. A coated on the Si, followed by annealing at 250 C for 1 h to
20 nm thick Cytop (Asahi Glass, Co. Ltd.) lm was then spin- form a hydrophobic Cytop/Si composite mold, as shown in
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Figure 4. (a) Representative optical image of 10 m wide graphene line pattern for electrical characterization. (b) Resistance per unit length
as a function of graphene line width, for a trench depth of 3 m. (c) Relative resistance of graphene lines as a function of bending radius
(bottom axis) and tensile strain (top axis) measured during bending. (d) Relative resistance of graphene lines over 1000 bending cycles at
0.5% and 1% tensile strain.

Figure 2a. The Cytop uorinated polymer coating exhibits a
low of 19 mJ/m2,47 corresponding to a large water contact
angle of 107 on our mold (Figure S3). This low surface energy
is comparable to that for conventional transfer printing molds
(25 mJ/m 2 for polyurethane acrylate, 20 mJ/m 2 for
polydimethylsiloxane),42,43 indicating that Cytop-coated Si
can provide a robust platform for transfer printing.
The graphene ink with of 33 mJ/m2 is introduced using a
pipet along the mold surface (Figure 2a). The ink selectively
lls the trenches, leaving no detectable residue on the top
surface of the hydrophobic mold due to its intermediate surface
energy in the range of 2570 mJ/m2 (see Supporting
Information). Earlier research identied a trench aspect ratio
(depth:width) of 1:51:20 for successful ink lling, with lower
values leading to ink beading up to minimize surface area.42,43
As shown in Figure S4, however, the graphene ink eectively
lls trenches with a very low aspect ratio of 1:2000, possibly
due to the low surface energy of the ink, leading to broader
design exibility for electronic applications. With this reliable
selective wetting and control of the print direction for trenches
of arbitrary length, lling the mold with graphene ink is readily
demonstrated (Movies S1S5).
The graphene ink in the thermally stable mold was then
annealed on a hot plate in air at 250 C for 30 min to produce a
conductive graphene lm. Because the nanosized graphene
akes are eectively stabilized by ethyl cellulose, partial
decomposition of this insulating polymer during the annealing
step yields a dense and continuous graphene network with an
electrical conductivity exceeding 104 S/m.34 Selective dewetting
and annealing steps were repeated four times to increase the
graphene lm thickness, thereby reducing the line resistance
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(Figures S5, S6). High-resolution scanning electron microscopy
(SEM) images of the graphene lines in the Cytop/Si mold are
shown in Figure 2b,d, conrming that the graphene inks leave
no visible residue on the mold surface, and the lines inside the
trenches remain continuous. Higher magnication SEM images
(Figure S7a) reveal a sharp graphene line edge and a at,
continuous lm of graphene akes on the Cytop/Si mold, with
sub-10 nm line edge roughness (Figure S8).
The annealed graphene lines were transferred to transparent,
exible PET substrates using a UV-curable adhesive, as shown
schematically in Figure 3a. First, a liquid prepolymer of
Norland Optical Adhesive (NOA73) with a viscosity of 130
mPas was coated on the annealed graphene lines in the Cytop/
Si mold, with a 10 min wait time to ensure reliable contact
between the viscous NOA73 solution and the graphene surface.
After bringing O2 plasma-treated PET into contact with the
NOA73-coated mold, the adhesive was cured upon exposure to
UV light (1000 W/m2) for 20 min. The annealed graphene
lines, now bonded to the cured NOA73 adhesive, are readily
peeled o from the Cytop/Si mold. The nal, transfer-printed,
high-resolution graphene lines on PET exhibit an inverted
structure replicated from the mold, and the process is highly
reproducible.
Characterization of the transfer-printed graphene lines on
PET is shown in Figure 3bd. The large-area SEM images in
Figure 3b conrm the successful transfer of graphene lines with
no defects or breaks. Moreover, 3D optical imaging (Figure 3c)
veries the spatial uniformity and shows no curling in the
NOA73 lm. In the high-resolution SEM image of Figure 3d,
the top surface of the high-resolution graphene patterns
exhibits low roughness. AFM imaging conrms this, with a
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Figure 5. (a) Photograph of selectively lled EGT patterns by the graphene ink. (b) Optical microscopy image of (a), with L and W of 20 and
400 m, respectively. (c) Schematic drawing of aerosol jet printing for EGT fabrication: (i) transferred graphene electrodes on PET; (ii)
P3HT semiconductor printing; (iii) ion gel dielectric printing; (iv) PEDOT:PSS gate connection printing. (d) Photograph of exible EGTs
printed on PET. (e) Optical image showing printed layers of source, drain, ion gel, and gate (the P3HT is dicult to see, but was printed
between source and drain electrodes below the ion gel).

root mean squared surface roughness of 9 nm over a 4 4 m2
area (Figure S9). This is considerably lower than the surface
roughness (3050 nm) resulting from gravure or screen
printing3436 and results from the templating of the exposed
graphene surface on the smooth Cytop/Si mold. In addition, a
sharp line edge (<25 nm in roughness) is measured for the
transferred graphene on PET (Figure S10). To demonstrate the
generality of this transfer printing method, a reactive silver ink48
was printed on PET substrates. As shown in Figure S7b, the
printed silver exhibits a well-dened line edge, with nano-
particle-like lm morphology that is notably dierent from that
of the graphene. SEM images (Figure S11) conrm that high-
E DOI: 10.1021/acsnano.7b03795
resolution transfer-printed silver features can also be realized,
suggesting process compatibility of this method with a range of
functional inks for high-resolution patterning on exible
substrates.
To perform electrical measurements, test patterns of
graphene were printed on PET with varying line widths and
lengths, as shown in Figure 4a. The linear t of line resistance
(R) versus length (L) shown in Figure S12 was used to calculate
the resistance per unit length (unit: k mm1) for a given line
width. The obtained values decrease with the graphene line
width (Figure 4b). The sheet resistance was calculated to be
470 80 / for 3.2 m lines and 35 6 / for 10 m
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Figure 6. (a) Transfer and (b) output characteristics of EGTs with graphene electrodes. (c) Threshold voltage (Vth) and eld-eect mobility
() of EGTs over 1000 cycles of bending at 1% tensile strain. (d) Dynamic response of a 1 M resistor-loaded inverter with a 50 Hz square
wave input signal.
lines, which is highly competitive with other printable
graphenes.49 Such resistances are suciently low for demon-
stration of nano- or micron-scale electronic devices. For large-
area applications such as extended interconnect lines, further
enhancement in conductivity while maintaining the advantages
of graphene electrodes could potentially be realized using a
combination of graphene and silver.50
To assess the mechanical stability of the transfer-printed
graphene lines, bending tests were performed. The adhered
NOA73 lm on exible PET serves as an excellent supporting
lm for the graphene line patterns without noticeable
delamination or other defects resulting from the bending
tests. The relative resistance of R/R0, where R0 is the resistance
without bending, is plotted with respect to strain () in Figure
4c. The bending strain was estimated by the relation = d/2r,
where d denotes substrate thickness (135 m) and r is the
bending radius, with the condition r d.51 The relative
resistance of printed graphene lines gradually increased during
bending for strain values up to 1%, with an abrupt increase to
1.4 at higher strains, at = 2.3%. The increase is apparently
arising from nanoscale fracture between graphene akes as
shown in a high-resolution image (Figure S13). When the
applied strain of 2.3% was removed, the relative resistance
values partially recovered to 1.25 and remained consistent upon
further cycling of the strain (Figure S14). To further assess the
bending fatigue tolerance of the graphene patterns, cyclic
bending tests were performed (Figure 4d). The rise in the
resistance of graphene is minimal over 1000 cycles with a strain
of 0.5%. Even at an increased strain of 1%, only a 5% increase
of the resistance is observed, compared with a 300% increase
in resistance for the Ag patterns (Figure S15). Considering the
line thickness (1 m), the obtained bending stability of
graphene is remarkable. Further enhancement in the
mechanical stability could potentially be realized by tailoring
the amount and nature of polymer residue in the lm.52 The
transfer-printed graphene lines therefore exhibit good bending
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tolerance, an important characteristic for application in exible
electronic devices.
Graphene electrodes are commonly used for organic
electronic devices due to the favorable physical and electronic
interface of graphene with organic semiconductors, including a
low contact resistance and stable electrical interface.35,36 Here
we utilize transfer-printed 10 m wide graphene electrodes to
fabricate all-printed, low-voltage electrolyte gated transistors
(EGTs) and inverters on plastic to demonstrate the utility of
this transfer printing method for exible electronics. The
electrolyte-based gate dielectric of EGTs is attractive for printed
electronics due to its process compatibility, mechanical
exibility, and high capacitance (>5 F/cm2), which allows
low voltage operation on exible substrates.44 The hydrophobic
mold for EGT source and drain electrodes was prepared with
the same method used for the line patterns. As shown in Figure
5a,b, selective dewetting by graphene ink was successful with
the EGT mold. After the annealing, the source and drain
graphene electrodes were transferred to PET, mediated by the
NOA73 adhesive. To complete the EGTs, aerosol jet printing
was employed to deposit the remaining electronically functional
inks (Figure 5c). These include poly(3-hexylthiophene)
(P3HT) as the semiconductor, an ion gel as the gate dielectric
(see Methods section for details), and poly(3,4-
ethylenedioxythiophene:poly(styrenesulfonate) (PEDOT:PSS)
as the gate electrode. The printed features on exible PET are
shown in Figures 5d,e, and the gate connection is shown in
Figure S16.
A p-type EGT was demonstrated with a P3HT semi-
conductor lm for which a 3D conducting channel was created
by electrochemical doping.44 Figure 6a presents the transfer
characteristics of the EGTs with graphene electrodes, showing
well-controlled transistor operation with negligible drain
current (ID) hysteresis. When the graphene electrodes with
good stability were replaced with the silver electrodes, the
resulting EGTs were unstable and showed signicantly
degraded performance even during the second measurement
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cycle (Figure S17), likely due to the oxidation reaction (e.g., Ag
Ag+ + e). This result emphasizes the superior interface
properties of the graphene electrode. The output characteristics
(Figure 6b) show clear ID saturation, resulting from pinch-o at
high drain voltages (VDS). Ohmic contact is evident by the
linear IV relationship at low VDS. The standard saturation
regime equation was used to calculate hole mobility () and
threshold voltage (Vth) from eq 1:53
W of a triblock copolymer, poly(styrene-b-methyl methacrylate-b-
ID = Ci (VG Vth)2
2L (1)
where Ci is the capacitance of ion gel dielectric, L is the channel
length, W is the channel width, and VG is the gate voltage. The
capacitance was measured to be 57 F cm2 for low-frequency
operation (Figure S18). The hole mobility and threshold
voltage were calculated to be 0.3 cm2 V1 s1 and 0.3 V,
respectively, with an on/o current ratio of 105, promising
performance metrics for sub-1 V, fully printed EGTs. Cyclic
bending of the EGTs to 1% strain over 1000 cycles resulted in
small shifts of 0.02 cm2 V1 s1 in mobility and 0.03 V in
threshold voltage, respectively (Figure 6c). Finally, a 1 M
resistor-loaded inverter was fabricated to evaluate the dynamic
response of the devices (see circuit diagram in Figure 6d). This
inverter switched well at 50 Hz, with the output voltage (Vout)
swinging between 1 and 0 V in response to the dynamic input
voltage (Vin).
In addition to improved device performance, high-resolution
printing oers increased packing density, with benets for
circuit integration for electronic applications. The device
footprint using graphene electrodes, dened by the substrate
area per transistor, is about 2.3 mm2, which is considerably
larger than that of the transistor working region (0.016 mm2).
This is mostly because contact pads (300 m in diameter)
were largely designed for measurement convenience. They can
be easily reduced in size to 10 m, resulting in a footprint of
0.043 mm2. This indicates that a high density of transistors
(2000 devices cm2) can be achieved by the transfer printing
method compared to previous methods such as screen printing
(50 devices cm2).35 Furthermore, shorter channel length of
1 m, enabled by the precision printing method with line
edge roughness below 25 nm, can be transfer printed using the
EGT mold to allow printing of 2500 transistors cm2 (Figure
S19), demonstrating the suitability of transfer-printed graphene
electrodes for printed electronic systems.
CONCLUSIONS
Overall, we have demonstrated here a transfer printing method
based on a hydrophobic Cytop/Si mold suitable for high-
resolution patterning of graphene inks. The robust thermal
stability of the mold (250 C) allows broad process
compatibility, enabling printing of conductive, exible, sub-5
m graphene patterns. Excellent conductivity and exibility of
the graphene electrodes are demonstrated and utilized for fully
printed EGTs tolerant to tensile strains of 1% over 1000
bending cycles. By leveraging the high-delity printing process,
capable of achieving line edge roughness below 25 nm, the
transistor channel length could be scaled to 1 m, oering a
compelling advantage for progress in the scalable fabrication of
nanoelectronic devices. This promising platform for transfer
printing oers signicant potential for expanding the design
space to integrate functional inks with precise, high-resolution
patterning methods, ultimately advancing the development of
high-performance, exible, printed electronic systems.
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METHODS
Materials. Cytop (CTL-809M; Asahi Glass Co., Ltd.), its solvent
(CT-SOLV180; Asahi Glass Co., Ltd.), and UV-curable adhesive of
NOA73 (Norland Products Inc.) were used as received. PET was
cleaned by 2-propanol and O2 plasma prior to use. Reactive silver ink
was synthesized according to the literature.48 The inks used for EGT
fabrication were prepared following the literature methods.35,36 In
short, the semiconductor ink was prepared by dissolving P3HT in
chloroform (1 mg mL1). The ion gel dielectric ink consists of 1 wt %
styrene) (PS-PMMA-PS) and 9 wt % of an ionic liquid, 1-ethyl-3-
methylimidazolium bis(triuoromethylsulfonyl)imide (EMITFSI) in
90 wt % ethyl acetate. The commercial PEDOT:PSS ink (PH1000,
Heraus) was further diluted by ethyl acetate at a blend ratio of 9:1 (w/
w). Graphene inks for line patterns and EGT electrodes were
synthesized according to the literature.35 In short, liquid-phase
exfoliation and occulation methods yielded a graphene-ethyl cellulose
powder (40 wt % graphene), and 2.0 g of this powder was directly
dispersed in a solvent mixture of 10 mL terpineol (Aldrich, mixture of
isomers, anhydrous) and 40 g ethanol (Koptec, 200 proof) under bath
sonication for 120 min at 35 C. A 3.1 m glass ber syringe lter
(Acrodisc) was used to lter the dispersion, and mild heating on a hot
plate resulted in removal of ethanol, thus producing a graphene ink,
comprising 20% w/v solids in terpineol, with a graphene:ethyl
cellulose ratio of 2:3 w/w. The shear viscosity of the ink was evaluated
to be 1000 mPas at room temperature. For transfer printing, the ink
was further diluted by 50% with cyclohexanone, yielding a viscosity of
150 mPas, below the threshold value (500 mPas) for selective
dewetting.43
Preparation of Hydrophobic, Patterned Molds. The silicon
wafer (100) was rst cleaned by O2 plasma before prebaking at 115 C
for 1 min. The silicon wafer was spin-coated with photoresist (Shipley
S1813) at 2000 rpm for 30 s, followed by postbaking at 115 C for 1
min. Then, a Karl Suss MA/BA6 was used to expose the photoresist-
coated wafer through a line or EGT patterned mask. After developing,
the patterned silicon wafer was dry-etched by reactive ion etching
(SLR 770 Deep Trench Etcher). The etched silicon wafer was
immersed in acetone and subsequently in piranha solution (mixture of
96 wt % H2SO4 and 30 wt % H2O2 in a ratio of 50:50) to remove the
photoresist. Caution! Piranha solution is a strong oxidizer, requiring
extreme caution while handling, and should not be stored in closed
containers. Then, O2 plasma was further applied to the patterned wafer,
before spin-coating Cytop solution with the volumetric ratio of 10:1
CTL-809M:CT-SOLV180 at 2000 rpm for 1 min. Finally, the Cytop-
coated, patterned silicon wafer was annealed in air at 250 C for 1 h.
Graphene Ink Printing. While dragging the graphene ink over the
Cytop/Si mold, the rate was maintained at 1 cm/s or lower. Higher
rates resulted in small droplets of ink remaining on the unetched
surface regions of the mold.
Device Fabrication. Aerosol-jet printing (AJ 200, Optomec) was
employed to fabricate the transistor and inverter. The deposition of
the P3HT semiconductor, ion gel dielectric, and PEDOT:PSS gate
electrode was carried out on PET with printed graphene source, drain,
and gate contact pads. A 150 m diameter nozzle was used for aerosol-
jet printing, and the carrier gas/sheath gas rates were 15 sccm/40 sccm
for P3HT and the ion gel and 20 sccm/40 sccm for PEDOT:PSS.
During aerosol-jet printing, the stage was maintained at 60 C. The
printer was enclosed in a vented acrylic box to minimize exposure to
the aerosol.
Characterization. For AFM characterization, SiO2 wafers were
cleaned prior to use by sonication in acetone and isopropanol,
followed by O2-plasma cleaning. Further dilution of the graphene ink
by cyclohexanone to yield 0.001 mg/mL solids was performed for
sparsely and uniformly coated graphene lm. The diluted ink was spin-
cast onto the wafers for 1 min at a spin speed of 2000 rpm. Then, the
graphene coated wafers were annealed in air at 400 C for 2 h to
completely remove the ethyl cellulose. A rheometer (AR-G2, TA
Instruments) with a parallel plate assembly and a drop shape analyzer
(Kruss DSA30) were used for shear viscosity measurement and for
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surface energy measurement, respectively. These measurements were
carried out at room temperature. The printed graphene lines were
characterized with a multimeter, optical microscope (KH-7700,
HIROX), and SEM (JSL-6500, JEOL). The IV performance of
EGTs was measured using two source meters (Keithley 236, 237) and
an electrometer (6517A, Keithley) in a nitrogen atmosphere at room
temperature. In order to record inverter performance, the input signal
of inverters was generated by an Agilent 33220 arbitrary-waveform
generator, and the dynamic response was collected by a Tektronix
TDS1002B digital oscilloscope.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b03795.
Additional experimental results, including Figures S1
S19 (PDF)
Movie S1: Line trench lling by vertically dragging
graphene ink at (droplet size) > (trench size) (AVI)
Movie S2: Line trench lling by horizontally dragging
graphene ink at (droplet size) > (trench size) (AVI)
Movie S3: No line trench lling by vertically dragging
graphene ink at (droplet size) < (trench size) (AVI)
Movie S4: Line trench lling by horizontally dragging
graphene ink at (droplet size) > (trench size) (AVI)
Movie S5: No line trench lling with water droplet
dragging (AVI)
AUTHOR INFORMATION
Corresponding Author
*E-mail: frisbie@umn.edu.
ORCID
Donghoon Song: 0000-0003-0914-1507
Mark C. Hersam: 0000-0003-4120-1426
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work was supported by the Multi-University Research
Initiative (MURI) program (N00014-11-1-0690) sponsored by
the Oce of Naval Research. Support from the Air Force
Research Laboratory under agreement number FA8650-15-2-
5518 is also acknowledged. Parts of this work were performed
at the Characterization Facility and the Nano-Fabrication
Center of the University of Minnesota. The authors thank Fazel
Zare Bidoky for experimental assistance and Chang-Hyun Kim
and Krystopher Jochem for helpful discussions. The U.S.
Government is authorized to reproduce and distribute reprints
for Governmental purposes notwithstanding any copyright
notation thereon. The views and conclusions contained herein
are those of the authors and should not be interpreted as
necessarily representing the ocial policies or endorsements,
either expressed or implied, of the sponsors.
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I DOI: 10.1021/acsnano.7b03795
ACS Nano XXXX, XXX, XXXXXX