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PUBLISHED ONLINE: 10 MAY 2009 | DOI: 10.1038/NMAT2459

Stretchable active-matrix organic light-emitting


diode display using printable elastic conductors
Tsuyoshi Sekitani1 , Hiroyoshi Nakajima2 , Hiroki Maeda2 , Takanori Fukushima3,4 , Takuzo Aida4,5 ,
Kenji Hata6 and Takao Someya1,7,8 *

Stretchability will significantly expand the applications scope of electronics, particularly for large-area electronic displays,
sensors and actuators. Unlike for conventional devices, stretchable electronics can cover arbitrary surfaces and movable parts.
However, a large hurdle is the manufacture of large-area highly stretchable electrical wirings with high conductivity. Here,
we describe the manufacture of printable elastic conductors comprising single-walled carbon nanotubes (SWNTs) uniformly
dispersed in a fluorinated rubber. Using an ionic liquid and jet-milling, we produce long and fine SWNT bundles that can form
well-developed conducting networks in the rubber. Conductivity of more than 100 S cm1 and stretchability of more than 100%
are obtained. Making full use of this extraordinary conductivity, we constructed a rubber-like stretchable active-matrix display
comprising integrated printed elastic conductors, organic transistors and organic light-emitting diodes. The display could be
stretched by 3050% and spread over a hemisphere without any mechanical or electrical damage.

R
ecently, new technologies have been emerging in stretchable SWNTrubber composite gel becomes increasingly viscous, and
electronics18 , motivating intensive efforts to grant various consequently this material can be finely patterned using direct
kinds of surface some form of intelligence917 . The largest printing technologies. Furthermore, a printed elastic conductor
obstacle, however, has been the development of stretchable or requires no extra coating and mechanical process, and can
elastic electrical wiring that is both highly conductive and highly stretch by 118% and has an extraordinarily high conductivity of
stretchable. Various types of high-conductivity stretchable ma- 102 S cm1 . To the best of our knowledge, this is the highest
terial have been developed, such as wavy thin metals17 , metal- value reported for a stretchable, printable conductor so far. This
coated net-films15 , graphene films18 and single-walled carbon printable elastic conductor can be used for stretchable wires
nanotubes19,20 (SWNTs)/fluorinated copolymer composite8 . These and contacts in electrical integrated circuits. We have integrated
stretchable materials exhibit excellent conductivity and mechanical such printed elastic conductors with organic transistors2427 and
stretchability by exploiting structures such as waves and nets; the organic light-emitting diodes28 (LEDs) to realize a truly rubber-
manufacturing process used is vacuum evaporation, photolitho- like active-matrix organic LED display. A 16 16 grid of
graphic patterning or mechanical punching and/or cutting. How- transistors was used for driving the display and the effective
ever, because these manufacturing processes are not scalable, it size of the active matrix was 10 10 cm2 . The display could
is difficult to apply to large-area electronics. One solution would be stretched by 3050% and spread over a hemisphere without
be the use of direct printing technologies using printable inks any mechanical or electrical damage. Furthermore, it remained
that have high conductivity and stretchability, but none has been functional even when folded in two or crumpled up, indicating
reported thus far. Our group has reported an elastic conductor excellent durability.
comprising SWNTfluorinated copolymer composite8 ; however,
the material was incompatible with printing owing to its low viscos- Stretchable, conductive inks
ity and tendency for reaggregation before drying and, furthermore, A schematic representation of the manufacturing process is shown
it required an extra rubber coating and mechanical process to in Supplementary Fig. S1. As a chemically stable and highly
improve the elasticity. conductive dopant, we used super-growth SWNTs of high purity
We have developed a printable elastic conductor comprising and with a high aspect ratio (>99.98% in purity, >1 mm in length
SWNTs uniformly dispersed in a highly elastic fluorinated and 3 nm in diameter)20 . Typically, a mixture of super-growth
copolymer rubber by using an imidazolium ion-based ionic SWNTs (30 mg), an ionic liquid (1-butyl-3-methylimidazolium
liquid2123 and a jet-milling process. Taking advantage of a process bis(trifluoromethanesulphonyl)imide, BMITFSI, 60 mg) and
that can uniformly disperse finer bundles of SWNTs in a rubber 4-methly-2-pentanone (20 ml) was stirred at 25 C with a
matrix without shortening the length of the nanotubes, the magnetic stirrer (>700 r.p.m.) for 16 h. The resulting swollen

1 Quantum-Phase Electronics Center, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan, 2 R&D Center, Dai
Nippon Printing Co., Ltd, 250-1 Wakashiba, Kashiwa-shi, Chiba-ken 277-0871, Japan, 3 Functional Soft Matter Engineering Laboratory, Advanced Science
Institute, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan, 4 Department of Chemistry and Biotechnology, School of Engineering, The University of
Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan, 5 Nanospace Project, Exploratory Research for Advanced TechnologySolution Oriented Research
for Science and Technology, Japan Science and Technology Agency, National Museum of Emerging Science and Innovation, 2-41 Aomi, Koto-ku, Tokyo
135-0064, Japan, 6 Research Center for Advanced Carbon Materials, National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565,
Japan, 7 Institute for Nano Quantum Information Electronics, The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8505, Japan, 8 Department of
Electrical and Electronic Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan. *e-mail: someya@ee.t.u-tokyo.ac.jp.

494 NATURE MATERIALS | VOL 8 | JUNE 2009 | www.nature.com/naturematerials


2009 Macmillan Publishers Limited. All rights reserved.
NATURE MATERIALS DOI: 10.1038/NMAT2459 ARTICLES
a a
100 Sample 1 (SWNT 15.8 wt%)

Conductivity (S cm1)
Sample 2 (SWNT 5.1 wt%)
100 m
10
Sample 3
(SWNT 1.4 wt%)

0.1
0 50 100 150
Stretchability (%)

b 120 120

c 100 100
b
Conductivity

Conductivity (S cm1)
Stretchability (%)
80 80

60 60

100 m 200 nm
40 40
Stretchability

20 20
Figure 1 | Printable elastic conductors. a, Printed elastic conductors on a
PDMS sheet. Printed elastic conductors patterned by screen printing can 0 0
0 5 10 15 20
be stretched by 100% without electrical or mechanical damage. The insets SWNT (wt%)
show SWNTs dispersed in paste and a micrograph of printed elastic
conductors with a linewidth of 100 m. The picture was taken without Figure 2 | Electrical and mechanical characteristics of printed elastic
stretching. b, An SEM image of the surface of printed elastic conductors. conductors. a, Conductivity of printed elastic conductors as a function of
SWNTs were uniformly dispersed in a fluorinated copolymer matrix stretchability. Typical elastic conductors with 15.8, 5.1 and 1.4 wt% SWNTs
(Daikin, Daiel-G912), which is a very soft rubber, using a room-temperature are shown. Conductivity increases with SWNT content, whereas stretcha-
ionic liquid (BMITFSI) and jet-milling. c, A magnified SEM image of the bility decreases. Furthermore, conductivity does not change with stretching.
elastic conductor. Finer or exfoliated bundles of SWNTs were uniformly b, Stretchability and conductivity as a function of SWNT content.
dispersed in the rubber, and formed well-developed conducting networks.
bundles of SWNTs were made much finer through the process
gel was processed on a high-pressure jet-milling homogenizer using ionic liquid and jet-milling. In fact, the SWNTs were sig-
(60 MPa; Nano-jet pal, JN10, Jokoh), giving a black paste-like nificantly untangled or exfoliated after the jet-milling process (see
substance, referred to as bucky gel. To the gel were successively Supplementary Fig. S2). We clearly demonstrated that the process
added 4-methly-2-pentanone (80 ml) and a fluorinated copoly- including an ionic liquid and jet-milling significantly untangled
mer, vinylidenefluoridetetrafluoroethylenehexafluoropropylene or exfoliated the bundle of SWNTs, and formed well-developed
(501,500 mg; Daiel-G912, Daikin; referred to as G912 henceforth), nanotube networks in a rubber, as shown in Fig. 1c.
and the mixture was stirred at 25 C for 16 h, poured onto a glass The electrical and mechanical properties of the printed elastic
plate by drop-casting and air dried for 6 h to afford a SWNTrubber conductors under tensile stress were investigated using a preci-
composite gel (referred to as SWNT paste henceforth; Fig. 1a). sion mechanical stretching system (Autograph AG-X; Shimazu).
The paste viscosity was approximately 10 Pa s. Furthermore, when Figure 2a shows a plot of the conductivity as a function of stretch-
the SWNT paste was air dried for more than 12 h, an elastic ability as the SWNT content was changed from 1.4 to 15.8 wt%.
conductor was formed. A SWNT content of 15.8 wt% produced an extraordinarily high
The SWNT paste was patterned on rubber sheets made of conductivity of 102 S cm1 and stretchability of 29%. In contrast,
a silicone elastomer (polydimethylsiloxane, PDMS; Sylgard 184, the conductors with 1.4 wt% SWNTs exhibited an extraordinarily
Dow-Corning) using screen printing through shadow masks. The high stretchability of 118% and conductivity of 9.7 S cm1 . Impor-
patterned SWNT pastes were air dried for more than 6 h to tantly, the elastic conductors did not show significant changes in
afford fine SWNT-based elastic conductors with a linewidth of conductivity or any sign of mechanical damage when fully stretched.
100 m (Fig. 1a). The resolution is currently limited by the adhesion For comparison, a conventional conducting rubber containing
between the SWNT paste and the PDMS substrate. The printed carbon particles was also tested. Although the stretchability of the
elastic conductors can be stretched by approximately 100% without conventional conducting rubber exceeded 150%, the conductivity
mechanical damage or delamination from the PDMS matrix. was as low as 0.1 S cm1 , which is insufficient for electronic circuit
Note that the stretchability can be enhanced when printed elastic applications. In fact, low conductivity of electrical wirings may
conductors are sandwiched between rubber substrates because result in a low-speed response, large voltage depression and large
encapsulation prohibits the elastic conductors from delamination. power consumption.
More detailed information on the printability can be found in There are three important factors determining the conductivity
Supplementary Information. and stretchability of the printable elastic conductors. The first is
Figure 1b shows an image of the surface of printed elas- the mixing ratio of SWNTs, the ionic liquid (BMITFSI) and the
tic conductors taken using a scanning electron microscope fluorinated copolymer matrix (G912). The SWNT content was
(SEM, S4300; Hitachi). The smooth surface confirms that the changed from 1.4 to 15.8 wt% (Fig. 2b) while the BMITFSI content

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2009 Macmillan Publishers Limited. All rights reserved.
ARTICLES NATURE MATERIALS DOI: 10.1038/NMAT2459

was maintained at twice the SWNT content. When the SWNT a Data-line Bias-voltage-line
content was greater than 6 wt%, the conductivity was higher than VData VBias
50 S cm1 , and the stretchability was less than 40%. In contrast,
at less than 6 wt% of SWNTs, the stretchability was higher than
50%, and the conductivity was less than 40 S cm1 . Importantly, we Scanning-line
found that the elastic conductors have very smooth surfaces and VScan
high film quality over the wide range of SWNT contents. This is OLED IOLED
due to the compatibility of the constituent materials, as described Trselector
later. Furthermore, Fig. 2b clearly indicates that the important Trdriver
parametersconductivity and stretchabilitycan be systematically Iselector C
controlled and tailored to the demands of electronic applications, Ground-line
although there exists a trade-off between the two parameters.
One method to achieve a better balance between conductivity
and stretchability would be the use of mechanical punching b 102 104
to form a net-shaped structure, although this manufacturing
process is more complex. 101
103
The second factor is the method used to exfoliate the bundles of

Current density (mA cm2)


1

Luminance (cd m2)


SWNTs and make them finer so that they are uniformly dispersed 102
in the elastic fluorinated copolymer matrix. Typical dispersing 101
techniques such as ultrasonication, grinder-milling and ball-milling 102 101
can make the bundles finer, but at the same time, they make
the SWNTs shorter, thus reducing the conductivity. We used a 103
1
jet-milling high-pressure homogenizer that breaks materials into
104
fragments with a high-pressure jet. It is particularly worth noting 101
that this process enables us to uniformly disperse finer bundles 105
of SWNTs into a rubber matrix without shortening the length 106 102
of the nanotubes during the process. The resulting longer and 0 5 10 15
finer bundles of SWNTs can form well-developed conducting Voltage (V)
networks in rubbers, as shown in Fig. 1c, thus leading to higher c VData = 50 V
IOLED
conductivity and stretchability, simultaneously. The formation of 103 40 V 103
SWNT networks in rubbers also realizes printability of this material 30 V
because the SWNT paste becomes increasingly viscous (more than 20 V
105 105
10 Pa s), which is very suitable for high-definition screen printing. 10 V
Besides the mixing ratio and dispersing process, the compati-
Iselector (A)

5 V

IOLED (A)
bility of the materialsSWNTs, ionic liquid and copolymersis 107 107
also very essential. We carried out material compatibility tests to
determine the combination of elastic polymers and ionic liquid that 109 109
would be compatible with each other (see Supplementary Fig. S3).
We examined three different fluorinated copolymers: G912 and 1011 1011
vinylidene fluoride/hexafluoropropylene copolymers with com-
position ratios of 0.78:0.22 (Daiel-G801, Mw = 150,000, Daikin; Iselector VBias = 30 V
1013 1013
referred to as G801 henceforth) and 0.88:0.12 (KYNAR-FLEX2801, 40 20 0 20 40 60
Mw = 30,000, Arkema; referred to as Kyner henceforth). G912 VScan (V)
is very soft and elastic, but this often results in separation of
the G912 and ionic liquid phases. We used BMITFSI, which is Figure 3 | Stretchable display cells comprising an organic LED and a 2T1C
compatible with several fluorinated copolymers. In fact, when G912 driving cell. a, Circuit diagram of one stretchable display cell comprising an
and BMITFSI were used, the resulting SWNT rubber films were organic LED and a 2T1C driving cell. Iselector and IOLED represent currents
very smooth, flat and uniform (Fig. 1b and Supplementary Fig. passing through the selector transistor Trselector and through the organic
S2c), and hence exhibited high conductivity and stretchability. LED, respectively. Display cells are interconnected with each other through
In contrast, when Kyner (which is a hard resin) was used, the printed elastic conductors that work as scanning-, data-, bias-voltage- and
resulting films exhibited a conductivity of only 21 S cm1 and ground-lines. VScan , VData and VBias represent voltages applied to scanning-,
were very fragile and not stretchable. When G801 (which is also data- and bias-voltage-lines, respectively. The capacitance of the circuit (C)
a soft rubber) was used, the conductors exhibited a stretchability is 215 pF. The resistor symbols represent printed elastic conductors.
of 87% and conductivity of 3 S cm1 with 1.8 wt% SWNTs, and b, Current density and luminance of a typical stand-alone organic LED as a
a stretchability of 24% and conductivity of 22 S cm1 at 15.7 wt% function of bias voltage. Experiments were carried out in ambient air.
SWNTs. The results of the compatibility tests convinced us that c, Iselector and IOLED as a function of VScan when VBias is constant at 30 V
combination of G912 and BMITFSI is the best from the points and VData is varied from 5 to 50 V.
of view of both the electrical and mechanical performance in the
process with jet-milling. produced by other groups2932 . In particular, Spinks et al. and
We also investigated the durability under stretching cycles. Shim et al. reported composites with excellent conductivities
Although durability depends on stretchability, the elastic con- of the order of 100 S cm1 by taking advantage of highly con-
ductors with 1.4 wt% SWNTs, 2.8 wt% BMITFSI and 95.8 wt% ductive polymers30,31 . Recently, Mukai et al. demonstrated the
G912 did not show changes in conductivity after 1,000 cycles fabrication of SWNT films comprising millimetre-long SWNTs
of stretching by 70%. and an ionic liquid, which also exhibited a high conductivity of
Carbon-nanotube-based conducting materials or carbon- 169 S cm1 (ref. 32). However, these materials reported so far
nanotube/conducting-polymer composites have also been cannot be stretched.

496 NATURE MATERIALS | VOL 8 | JUNE 2009 | www.nature.com/naturematerials


2009 Macmillan Publishers Limited. All rights reserved.
NATURE MATERIALS DOI: 10.1038/NMAT2459 ARTICLES
a
VScan +40 V 5 V 10 V 30 V 40 V

6.7 nA 1.7 A 35 A 381 A 1.3 mA

Cu wiring

0.0 cd m2 0.3 cd m2 6.1 cd m2 88.3 cd m2 408 cd m2

7.0 nA 1.6 A 31.6 A 343 A 1.2 mA

Elastic conductor

0.0 cd m2 0.28 cd m2 5.5 cd m2 77.2 cd m2 364 cd m2


2.6 nA 280 nA 6.6 A 19.4 A 40 A

Conventional conducting rubber

0.0 cd m2 0.0 cd m2 1.2 cd m2 3.4 cd m2 7.1 cd m2

Figure 4 | Luminance of a stretchable display. a, Luminance of a display cell as a function of VScan . Luminance was investigated for three configurations of
display cell: 1, an organic LED integrated with a 2T1C driving cell and electrical wirings made of 1- m-thick Cu; 2, an organic LED integrated with a 2T1C
driving cell and electrical wirings made of printed elastic conductors (conductivity, 50 S cm1 ; length, 100 mm; linewidth, 500 m; thickness, 100 m);
3, an organic LED integrated with a 2T1C driving cell and electrical wirings made of conventional conducting rubber (conductivity, 0.1 S cm1 ; length,
100 mm; linewidth, 1 mm; thickness, 100 m). VBias and VData were 30 V and 40 V, respectively. IOLED and luminance are also shown. The effective size
of the light-emitting area was 3 4 mm2 . b, A demonstration of a stretchable display that can be spread over arbitrary curved surfaces. The stretchable
display is functional even when folded in two or crumpled, indicating excellent durability.

We previously demonstrated the SWNTs were uniformly of SWNTs in the very elastic rubber matrix. The ionic liquid has the
dispersed in a fluorinated copolymer rubber matrix by grinding important role of plasticizing agents in the elastic conductors. This
with an imidazolium ion-based ionic liquid and the fabrication of enables the SWNT content to be increased up to 16 wt% without
a SWNTrubber composite with a conductivity of 57 S cm1 and reducing the mechanical flexibility or softness of the copolymer,
a stretchability of 134% (ref. 8). However, the previous composite G912 (see Supplementary Fig. S5).
could not be printed owing to its low viscosity and tendency for
reaggregation before drying and, furthermore, it required an extra Stretchable active-matrix display
rubber coating and mechanical process to improve the elasticity. Taking full advantage of printable elastic conductors with excellent
In this work, we found that through the process, the SWNT paste conductivity and stretchability, we manufactured a rubber-like
becomes increasingly viscous (more than 10 Pa s), and consequently stretchable active-matrix organic LED display comprising 16 16
this material can be finely patterned using direct printing driving cells with two organic transistors and one capacitor (2T1C),
technologies. The spatial resolution of the printing is approximately organic LEDs, elastic conductors and pastes. The manufacturing
100 m on PDMS substrate (see Supplementary Information). processes for the organic 2T1C driving cells and organic LEDs
Furthermore, the new material requires no extra coating and can be found in Supplementary Information. A circuit diagram
mechanical process, and exhibits the highest conductivity reported of one display cell with a 2T1C driving cell and an organic
for a stretchable conductor so far. It can be stretched by more LED is shown in Fig. 3a. Each driving cell comprises a selector
than 100% and, more importantly, it has an extraordinarily high transistor (Trselector ), a driver transistor (Trdriver ), a capacitor
conductivity of 102 S cm1 , which changes negligibly little with (C) and printed elastic conductors: selector transistors enable
stretching (Fig. 2 and Supplementary Fig. S4). Importantly, the addressing of each organic LED for light emission, and the
performance can be easily controlled by changing the mixing ratio. driver transistors control the luminance. Capacitors have a
This is mainly due to the use of jet-milling as well as ionic liquid major role for stabilizing light emission with high-frequency
that could prevent unfavourable aggregation of nanotube bundles, operation (see Supplementary Fig. S9). After manufacturing the
thus resulting in the uniform dispersion of finer and longer bundles organic LEDs and organic driving cells independently on separate

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2009 Macmillan Publishers Limited. All rights reserved.
ARTICLES NATURE MATERIALS DOI: 10.1038/NMAT2459

PDMS sheets, the two sheets were laminated to construct a or electrical damage because of the excellent conductivity and
rubber-like stretchable display. mechanical durability of the printed elastic conductors, organic
An active matrix comprising a sheet of 16 16 driving transistors and organic LEDs manufactured on the PDMS rubber.
cells was fabricated on a flexible polyimide film using vacuum Miniaturization of display cells for a higher resolution is, of
evaporation. These cells were mechanically processed to isolate course, one of the most important requirements. We successfully
and uniformly distribute them on a stretchable PDMS rubber patterned printable elastic conductors with linewidths of 100 m
sheet. The periodicity is 5 mm. Each isolated driving cell on using screen printing. However, screen printing can be used
the PDMS sheet was electrically connected using printed elastic to pattern pastes to resolutions of 10 m. Organic LEDs can
conductors as scanning-, data-, bias-voltage- and ground-lines be manufactured using printing technologies33 , and furthermore,
(Fig. 3a). The organic transistors for both Trselector and Trdriver had printing technologies of organic semiconductors and electrodes
a 50-nm-thick pentacene channel and 250-nm-thick parylene gate with resolutions of 1 m have been reported3436 .
dielectric layers; the channel length and width were 20 m and The stretchable materials and integration technology used in
6 mm, respectively. The manufactured organic transistors exhibited this study can also be used to create other types of functional
a mobility of 0.3 cm2 V1 s1 and an on/off ratio of 106 . Details electronics such as a rubber-like electrical artificial skin with an
of the transistor performance characteristics can be found in integrated, stretchable active matrix and pressure sensors14,15 or
Supplementary Information (see Supplementary Fig. S7). a rubber-like mechanical actuation system with an integrated,
Figure 3b shows the typical current density and luminance of an stretchable active matrix and actuators that can create the
organic LED as a function of the applied voltage. From 0 to 15 V, sensation of touch electrically16,17 . The combination of stretchable
the luminance increased to more than 5,000 cd m2 , indicating sensors, actuators and displays can be used to create real,
excellent light-emission characteristics. An encapsulation layer tangible displays and user-friendly humanmachine interfaces
made of plastic barrier films acted as an excellent gas barrier so on all kinds of surface. In this manner, the printable elastic
that the organic LEDs were not degraded even when operating in conductor developed in this work enables the construction of
ambient air; the lifetime in air is at least three months. electronic integrated circuits that can be spread over any surface,
The electrical characteristics of a 2T1C driving cell with printed including arbitrary curved surfaces and movable parts. This
elastic conductors were also investigated. Figure 3c shows plots of would significantly expand the areas where electronics can be
the currents through a selector transistor (Iselector ) and a driver used. This is an important step towards the development of the
transistor and organic LEDs (IOLED ) as functions of the voltage infrastructure for the imminent era of ambient electronics, in which
from scanning-lines (VScan ) when the voltages of the data-lines a multitude of electronic devices such as ambient sensors, actuators
(VData ) were gradually changed from 5 to 50 V; the bias and display networks function as user-friendly humanmachine
voltage of the organic LEDs (VBias ) was constant at 30 V. interfaces that can be used in daily life to enhance security,
Iselector is very small because the drain electrodes of the selector safety and convenience.
transistors were not grounded, whereas the selector transistors
can supply the voltage VData to the gate electrodes of the driver Received 13 March 2009; accepted 16 April 2009;
transistors. Therefore, when one selector transistor is addressed, published online 10 May 2009
the connected driver transistor is activated. In fact, IOLED increased
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Acknowledgements
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