Nnano 2011 36
Nnano 2011 36
Nnano 2011 36
Devices made from stretchable electronic materials could be incorporated into clothing or attached directly to the body.
Such materials have typically been prepared by engineering conventional rigid materials such as silicon, rather than by
developing new materials. Here, we report a class of wearable and stretchable devices fabricated from thin films of aligned
single-walled carbon nanotubes. When stretched, the nanotube films fracture into gaps and islands, and bundles bridging
the gaps. This mechanism allows the films to act as strain sensors capable of measuring strains up to 280% (50 times
more than conventional metal strain gauges), with high durability, fast response and low creep. We assembled the carbon-
nanotube sensors on stockings, bandages and gloves to fabricate devices that can detect different types of human motion,
including movement, typing, breathing and speech.
C
onventional electronic devices, fabricated on rigid but brittle 150% strain), fast response (delay time, 14 ms) and low creep
semiconductor wafers, have evolved through a drive towards (3.0% at 100% strain). These important features allow the material
miniaturization with a view to realizing faster, smaller and to be used to precisely monitor large-scale and rapid human
more integrated devices. An alternative approach to future electronics motion, as was demonstrated by embedding various strain sensors
is to integrate the attributes of flexibility and stretchability to realize into clothing worn over the skin then using it to detect movement,
soft1–9 and human-friendly devices8–10. Stretchability—the ability to typing, breathing and phonation (speech).
conform to and cover movable and arbitrarily shaped objects—
could be exploited in the development of wearable devices8–10 that Carbon nanotube film strain sensor
can be embedded into clothes and garments or even attached directly Figure 1a schematically illustrates the key processes in fabricating
to the skin. Possible applications of this include the detection of and operating a SWCNT film strain sensor. Vertically aligned and
human motion, monitoring personal health and therapeutics. very sparse (3–4% occupancy) SWCNT thin films (height, 1 mm;
Owing to the difficulties in developing stretchable electric thickness, 6 mm; length, 16 mm) were first grown from patterned
materials, the current mainstream strategy in attempting to catalysts using water-assisted chemical vapour deposition13. To
achieve stretchability is not to develop new materials, but instead make long films of arbitrary length, films were individually
is to engineer new structural constructs from established materials1. removed and laid side by side, with a 1 mm overlap, onto a flat elas-
For example, ultrathin silicon structures formed into buckled geo- tomeric dog-bone-shaped substrate (poly(dimethylsiloxane),
metries offer stretchability, and the strain applied to the device is PDMS; thickness, 1 mm), with the alignment of the SWCNTs
absorbed by deformation of the silicon structures1. Consequently, arranged perpendicular to the strain axis (Fig. 1b). For each iter-
the functional materials are exposed to a minimal amount of ation, the film was wet with a droplet of isopropyl alcohol, which
harmful strain. Various stretchable devices have been created flattened the film (thickness, 400 nm) to the substrate in a
using this approach, including conductors, transistors, diodes, manner similar to deflating an air mattress; this allowed the
photodetectors and integrated systems containing conventional SWCNTs to be packed into a highly densely packed solid form
rigid materials2,3, with the advanced functions and properties (density, 0.46 g cm23; occupancy, 42%; SWCNT spacing,
characteristic of modern semiconductor technology. 4.1 nm)14,15. This process resulted in the development of a strong
A different approach is to assemble a device from stretchable van der Waals contact with the substrate, achieved without any
materials. Examples of stretchable materials include polymer com- additional mechanical pressure. The adhesion strength was
posites with conductive fillers8,11 and extremely thin metal films measured as 12 N cm22 and was sufficient to bear large strain.
on stretchable polymer substrates12. In such stretchable devices, Representative resistivity–strain data recorded for the device in
the functional materials themselves are directly exposed to strain Fig. 1b showed a monotonic increase up to 280% strain (strain
and therefore stretched. This feature offers a unique opportunity speed, 1 mm min21) (Fig. 1c), at which point the PDMS substrate
to measure the strain-dependent change in device performance to ruptured. This monotonic increase in resistivity with strain demon-
monitor motion, for example of the human body. strates the potential use of this device as a gauge to measure strains
Here, we introduce a new type of stretchable electric nanomater- much higher than the 5% limit of conventional metal strain gauges
ial consisting of aligned single-walled carbon nanotube (SWCNT) (Fig. 1c). Strain gauges register resistance changes when stretched,
thin films13–15 that deform when stretched in a manner similar to and are used to measure acceleration, pressure, tension and strain.
the structural deformation of a string cheese when peeled. In this The most commonly used strain gauge consists of a non-stretchable
way we realized a novel strain sensor that can measure and with- metal foil, which, on stretching, deforms to become narrower and
stand strain up to 280%, with high durability (10,000 cycles at longer, resulting in an increase in resistance16. The use of a
1
Nanotube Research Center, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, 305-8565, Japan, 2 Japan Science and
Technology Agency (JST), Kawaguchi, 332-0012, Japan. * e-mail: kenji-hata@aist.go.jp
Strain sensor
SWCNT films
SWCNT films and in IPA
stretchable substrate
f 40
100
35
in resistance (%)
Relative change
Aligned direction 40 80
Strain (%)
112
30 38.4
104 60
36.8
Sensor under strain 25 96
35.2 40
c 500 20 33.6 88
10 20
0.5 1.5 2.5 3.5 4.5 5.5
15 0
400 0 1 2 3 4 5 6
5
in resistance (%)
Relative change
Time (s)
300 g 6
0 11
0 4 8
5
in resistance (%)
200
Relative change
Strain (%)
10
Aligned SWCNTs 4
100 Random SWCNTs 9
Metal strain gauge 3
0 8
0 100 200 300 2
Strain (%) 7
0 1 2 3 4 5
d 60 Time (s)
80
50 h 6
75 11
in resistance (%)
Resistance (k )
Relative change
in resistance (%)
40 5
Relative change
70
10
Strain (%)
30 4
65
30 9
20 3
60
8
10
20 55 2
0 10 20 7
0
0 50 100 150 200 4.6 4.7 4.8 4.9 5.0
Strain (%) Time (s)
e 40 i 20
90
35
Sensor 3
in resistance (%)
30 15
in resistance (%)
Relative change
Resistance (k )
Relative change
25 PDMS 85
20 Sensor 2 10 packaging
15 10th SWCNTs
10 Sensor 1 100th 5 80
1,000th PDMS
5 10,000th Electrode
0 0
50 100 150 200 0 40 80 120 160
Strain (%) Strain (%)
Figure 1 | SWCNT-film strain sensor. a, Key steps in fabricating the SWCNT strain sensor. b, Photograph of the SWCNT-film strain sensor under strain.
c, Relative change in resistance versus strain for the strain sensor (aligned SWCNTs, red), randomly oriented SWCNTs (blue) and conventional metal thin
film (black). Inset: close-up of the low-strain region. d, Relative change in resistance for the initial loading (red) and unloading (blue) cycle. Inset: enlarged
unloading plot. e, Relative change in resistance versus strain for multiple-cycle tests: 10 (red), 100 (blue), 1,000 (green) and 10,000 (black) cycles at
5–100% (sensor 1), 5–150% (sensor 2) and 5–200% (sensor 3) strain. The baselines of sensors 2 and 3 are raised by 5 and 10%, respectively. f, Relative
change in resistance (blue) in response to a 5–100% step function of mechanical strain. Inset: close-up of the overshoot. g, Relative change in resistance
(blue) during 2.5 Hz frequency cycling between 2.0 and 5.4% strain (red). h, Close-up of the final cycle of g. i, Initial loading (red) and unloading (blue)
of relative change in resistance versus strain for the packaged sensor. Inset: image of the packaged sensor structure.
non-stretchable metal foil limits device performance, highlighting (strain speed, 6 mm s21) differed in the loading and unloading
that the high deformability of SWCNT films results from its fibre phases (Fig. 1d). The unloading behaviour (Fig. 1d, blue line) was
structure, as discussed later. The resistivity behaviour observed characterized by two linear regions (strain of 0 to 40% and 60
during the first loading–unloading cycle and subsequent cycles to 200%) with different slopes. The slope reflects the gauge factor
a b c d e
0% 25% 50% 75% 100%
Island Gap
Initial strain
f g
Buckling
is
ax
a in
Str
h i j
Suspended SWCNT bundle 8 Island width
Gap width
Distance ( m)
4
k
2
0
0 20 40 60 80 100
Gap
Strain (%)
Figure 2 | Fracturing mechanism of film. a–e, Images of the SWCNT film on initial loading. Scale bar, 100 mm. f, SEM image of the fractural structure of the
SWCNT film at 100% strain. Scale bar, 5 mm. Inset: three-dimensional image at 100% strain. g, Low-resolution SEM image of homogeneous fracturing of the
SWCNT film. Scale bar, 50 mm. h, SEM image of the suspended bundles. Scale bar, 1 mm. i, Average island width (blue) and gap (red) versus strain for initial
loading. Error bars indicate standard deviation. j,k, Paper model of the unstrained and strained states, respectively.
(the sensitivity of the SWCNT film to strain), which is defined as compression. The strain sensor (length, 5 mm) was first twisted
(dR/R)/(dL/L), where R is resistance and L is length. The gauge while measuring resistivity (Supplementary Fig. S2). The relative
factors were calculated to be 0.82 (0 to 40% strain) and 0.06 change in resistance at 908 twist was 0.5%, corresponding to strain
(60 to 200%); in comparison, conventional metal gauges have a of 2%. The strain sensor was then subjected to normal mechanical
factor of 2.0 (5% maximum strain)16 and polymer composites strain across the sensor face using a 1-cm-radius pressure head and a
(thermal plastic elastomer) with 50 wt% carbon black a factor of static mechanical analyser to load compressive stress while measur-
20 (80% maximum strain)8. Our carbon-nanotube strain sensor ing the resistivity (Supplementary Fig. S2). The relative change in
exhibited excellent durability and stability, even at high strain levels resistance at 30% compression was 1%, corresponding to 3%
(100, 150 and 200% at a strain speed of 6 mm s21). At 100 and strain. These results demonstrate that the strain sensor has a high
150% strain, the strain sensor electrical response remained nearly selectivity against other types of deformation.
unchanged after 10,000 cycles (Fig. 1e). At 200% strain, the sensor Further tests were carried out to investigate environmental effects
was stable for 3,300 cycles, until the substrate ruptured, showing such as temperature and humidity. First, by its nature, the strain
that the performance was limited by the substrate. sensor is sensitive to temperature, because the expansion/shrinkage
Additional important advantages of the carbon-nanotube strain of the substrate caused by variation in temperature will be detected
sensor include its low creep and fast response. The sensor was as a strain by the sensor. When the temperature was raised from
cycled between 5 and 100% strain at a speed of 10.6 mm s21 and room temperature to 50 8C, the relative change in resistance was
with a recovery time of 5 s (Fig. 1f, red line). The response of the 6%. This effect was observed as a slow drift in resistivity that can
carbon-nanotube strain sensor to this strain (Fig. 1f, blue line) was be corrected practically using a.c. measurements or, more precisely,
fast, with a low overshoot of 3.0% and recovery time of 5 s. This compensated directly using a temperature monitor. Second, any
is markedly different from the 8.8% overshoot and more than environmental effect that influences the conductivity of carbon
100 s recovery time observed for polymer composites with conduc- nanotubes would also influence the strain sensor. For example,
tive fillers, even with a three times lower strain speed8. To evaluate the exposure to gases is well known to dope carbon nanotubes and
delay time, the nanotube strain sensor was subjected to a sinusoidal change their conductivity. When the strain sensor was exposed to
strain. The electrical delay was evaluated to be 14 ms (Fig. 1g,h; an exhaled breath (Supplementary Fig. S3), the resistivity changed
Supplementary Fig. S1). To the best of our knowledge, this is the by 0.6%, correspondsing to 2% strain.
only reported delay time on the order of milliseconds in this kind Packaging is therefore important in reducing the sensitivity of the
of large strain gauge to date. strain sensor to environmental effects and to prevent damage from
Several tests were performed to clarify the selectivity of the strain abrasion. To address this, the strain sensor was sealed with a PDMS
sensor to other types of deformations, such as twist and coating. Importantly, when sealed, the behaviour of the strain sensor
Gap Island
Strain unloading Strain loading
f 6 g
R1 R2
5
Distance ( m)
4
RC
3
1 R2 R1
Island width
Gap width
0
0 20 40 60 80 100
Strain (%)
Figure 3 | Properties of SWCNT film. a–e, Film surface morphology during the unloading–loading cycle. Scale bar, 100 mm. f, Average island width (blue) and
gap (red) versus strain for cycling following the conditioning step. Error bars indicate standard deviation. g, Model of the basic circuit of the film.
(Fig. 1i) was similar to that of the unsealed sensor, with only a slight Fracturing mechanism of carbon nanotube film
decrease in the gauge factor (0.05). Moreover, the sealed strain To understand the underlying mechanism of the film stretchability,
sensor showed improved linearity, with a linear increase in resis- we examined the structural change in the SWCNT film under differ-
tivity observed up to 150% strain. ent levels of strain (Fig. 2a–e; Supplementary Movie 1). On initial
There have been several reports of the individual strengths and stretching, irreversible fracturing throughout the film created gaps
advantages of other stretchable materials, but no material has and islands; with further strain, their numbers and also the gap
achieved this level of stretchability and durability, as well as a fast widths increased (Fig. 2f–i), explaining the observed linear increase
response and low creep. For example, a polymer composite in resistivity (Fig. 1d). Uniformity of the SWCNT film was vital for
(thermal plastic elastomer) with conductive material (carbon homogeneous fracturing throughout the film (Fig. 2g). In addition,
black, 50 wt%) has been assembled into textiles to measure large the film showed buckling parallel to the strain axis, because it fol-
strains (80%)8. This composite material has a large interfacial area lowed the same positive Poisson’s ratio as the substrate; that is,
and therefore friction, leading to long delays (recovery time above the substrate width narrowed as strain was applied (Fig. 2f ).
100 s, versus 5 s for the present arrangement) and creep (8.8% Importantly, suspended SWCNT bundles bridging the gaps
versus 3.0%). Thin metal films on flexible and stretchable polymer (Fig. 2h; with an appearance similar to peeled string cheese) were
substrates rupture into connected islands, and have been used as created, preventing film rupturing. This highlights the importance
strain sensors up to 60% strain12. However, their delay time was of the alignment of the SWCNTs in allowing exceptional strain tol-
over 40 s at 0.5% strain12. Several reports have used composites of erance compared with randomly oriented vacuum filtrated SWCNT
carbon nanotubes and polymers as strain sensors, and the results buckypaper (5% failure strain). Lateral interconnections between the
are summarized in Supplementary Table 1. Although some of SWCNTs were essential to create the suspended bundles, and milli-
those sensors had a large gauge factor (15), they only tolerated a metre-scale SWCNTs produced durable and elongated bundles
small maximum strain (1%). A multiwalled carbon-nanotube spanning wide gaps. The islands, in contrast, acted as anchors to
forest was infiltrated with polyurethane (PU) to make a conducting prevent film detachment. As demonstrated using a stretchable
polymer composite that was more stretchable (1,000%) than PU paper model (Fig. 2j,k), the mechanism of stretchability is analogous
alone17. However, the large drift in resistance over repeated to the structural deformation of the open-mesh geometries used to
loading–unloading cycles and probable large delay time owing to wrap three-dimensional objects, such as eggs4. When the paper film
the large interfacial area of the carbon nanotubes and polymer was stretched, open holes deformed to allow stretching (Fig. 2k),
would hinder its use as a strain sensor17. No reported sensors while the strips acted as bending units. This process was downsized
have shown a performance level comparable to the sensor reported by a factor of 2,000 for the SWCNT film, with suspended bundles
here in terms of maximum strain, durability, creep and delay time. acting as the bending units.
The nanotube strain sensor can be regarded as a cross between
thin-film-based strain sensors and composite strain sensors, where Repeated loading–unloading cycle properties
the conducting filler material is not infiltrated, but is instead The structural deformation (Fig. 3a–c) observed during the first
coated onto the surface of the polymer, thereby combining the unloading phase and subsequent loading–unloading cycles differed
strengths of both systems. This configuration provides a minimum significantly. During the subsequent phases (Fig. 3c–e), new gaps
interfacial area between the nanotubes and the polymer, thereby and islands were neither created nor annihilated, as demonstrated
minimizing the friction18 that causes delay, creep and durability. by the unvarying widths of the islands with strain (Fig. 3f ).
In fact, our preliminary analysis showed that delay and creep were Instead, all of the strain was absorbed by a reversible opening and
dominated by the substrate properties (Supplementary Fig. S4), closing of the gaps (Fig. 3a–e; Supplementary Fig. S5, Movie 1).
suggesting that the nanotube strain sensor could be further The reversible fracturing of the SWCNT film not only explained
improved. In contrast to traditional stretchable conducting the extreme level of stretchability, but was also key to the exceptional
materials, these results demonstrate that the nanotube strain durability, as demonstrated by the 10,000 cycle durability test
sensor has the potential to precisely monitor rapid and large-scale (Fig. 1e), which showed little degradation. The resistance of the
human motion. film increased monotonically (Fig. 1e) but not linearly with strain,
resistance (%)
b 2
d SWCNT rubber PDMS glue
change in
Strain sensor SWCNTs
Relative
0 Support
electrode PDMS
Bandage −2 Strain sensor
0 20 40 60
Time (s)
c
resistance (%)
0
change in
Relative
Stocking
−2
0 40 80 120
Time (s)
e f Strain sensor g
Little
Ring
Middle
Jumping Index
5%
100%
0 20
Time (s)
Figure 4 | Stretchable wearable devices. a,d,f, Photographs of a bandage strain sensor (a), a strain sensor fixed to a stocking (d) and a data glove (f). Inset
to a: Photograph of the sensor adhered to the throat. Inset to d: close-up of the device. b,c,e,g, Relative changes in resistance versus time for breathing,
phonation (speech), knee motion and data glove configurations, respectively.
and was characterized by two consecutive regions with different Adhesive bandages are used daily to protect small wounds and
gauge factors. To understand this resistivity behaviour, we devel- adhere securely to the body and conform to every contortion of
oped a simple model to describe the resistance of the fractured the skin. As a result of the stretchable device architecture, the
film (Fig. 3g): skin, bandage and SWCNT film device behave as a single cohesive
stretchable object, so deformation of the skin can be monitored
R1 Rc + 2R1 R2 + R2 Rc directly and precisely using the SWCNT film (Fig. 4a). When
R= (1)
R1 + 2Rc + R2 fixed to the chest, respiration could be monitored by the upward
and downward slopes of the relative resistance associated with inha-
where R1 , R2 and Rc are the resistances of the island, gap and sus- lation and exhalation (chest expansion and contraction) (Fig. 4b). In
pended bundle, respectively. Physically, suspended bundles are ana- contrast, when attached to the throat (Fig. 4a, inset), the device
logous to wires, and Rc (bridge elongation) should increase linearly monitored phonation (speech) by detecting motion of the laryngeal
with strain. Therefore, at large strain, when R2 ≫ R1 and Rc , prominence (the Adam’s apple) (Fig. 4c). Such devices might be
equation (1) becomes R ¼ 2R1 þ Rc . R1 , and Rc can be determined useful in a breathing monitor for the early detection of sudden
by fitting to experimental data (Supplementary Fig. S6) (R1 ¼ infant death syndrome (SIDS) in sleeping infants, alerting parents
37.6 kV; Rc ¼ 28.0 × strain (%) V). Thus, by knowing R1 and to any potential problems19.
Rc , the value of R2 is shown to increase exponentially with In the basic act of walking, the skin on the feet, waist and joints
strain (Supplementary Fig. S6) (R2 ¼ 147.9 × exp(0.0515 × strain repeatedly stretches and contracts by as much as 55%
(%)) kV). The good agreement between model and experiment (Supplementary Fig. S7), which already exceeds the limits (5%)
(Supplementary Fig. S6) allows us to gauge the resistance to absolute for conventional strain sensors. To detect large-scale human
strain. From these results, we interpret the double gauge factor be- motion, we seamlessly connected small films to fabricate a large
haviour of the resistance of the strain sensor as deriving from a SWCNT strain sensor with extended sensing area. Eight films
shift in the dominant contributions from gap opening (R2) under were connected together to form a 10 cm × 1 mm SWCNT film
low strain, to bridge elongation (Rc) under high strain. assembled on a commercial stocking (Fig. 4d) over the knee joint.
The large SWCNT film was necessary to detect and distinguish
Application in human motion detection every movement of the knee. As the knee joint moves in one direc-
To demonstrate the potential of the SWCNT films in wearable tion (as well as swivelling on its axis), the knee constantly rolls and
devices8–10, we fabricated a stretchable human motion detector by glides during movement, so the deformation site of the skin is con-
connecting stretchable electrodes to the films and assembling stantly varying. Although it was made from just one sensor, the
them on bandages and clothing. To avoid mechanical failure at the device could easily detect, and also discriminate, various human
junction between the stretchable SWCNT film and rigid electrodes, motions related to the extension and flexion of the knee, including
we used SWCNT conductive rubber paste5,6 to fabricate the bending, marching, squatting and jumping, and combinations of
stretchable electrodes and a PDMS rubber glue (SH-780) to assem- these (Fig. 4e; Supplementary Movie 2). For example, the complex
ble the components onto the target material (bandage, clothing, and motion of explosive jumping using a squatting motion could be
so on). The SWCNT conductive paste was fabricated by dispersing clearly determined from the initial knee flexing (upward slope),
highly elastic fluorinated copolymer rubber into a SWCNT gel. This quick knee extension (downward slope), slight flexure from the
gel was composed of millimetre-long SWCNTs and an ionic liquid landing (second upward slope) and recovery (final downward
mixed by a high-pressure jet-milling homogenizer. This SWCNT slope). One advantage of using clothing-integrated devices is the
rubber paste was painted on the ends of the SWCNT film and option for repeatable and sharable use of the sensor. In addition,
dried to form an elastic conductor. Finally, the PDMS glue was this device does not restrict motion, in contrast to conventional
used to cover the electrodes, both for reinforcement and to fix the rotary encoders, and would therefore be beneficial for human-
device onto a commercial adhesive bandage. friendly rehabilitation20.