ARTICLES

PUBLISHED ONLINE: 11 NOVEMBER 2012 | DOI: 10.1038/NNANO.2012.192

An electrically and mechanically self-healing

composite with pressure- and flexion-sensitive
properties for electronic skin applications
Benjamin C-K. Tee1†, Chao Wang2†, Ranulfo Allen2 and Zhenan Bao2 *

Pressure sensitivity and mechanical self-healing are two vital functions of the human skin. A flexible and electrically
conducting material that can sense mechanical forces and yet be able to self-heal repeatably can be of use in emerging
fields such as soft robotics and biomimetic prostheses, but combining all these properties together remains a challenging
task. Here, we describe a composite material composed of a supramolecular organic polymer with embedded nickel
nanostructured microparticles, which shows mechanical and electrical self-healing properties at ambient conditions. We
also show that our material is pressure- and flexion-sensitive, and therefore suitable for electronic skin applications. The
electrical conductivity can be tuned by varying the amount of nickel particles and can reach values as high as 40 S cm21.
On rupture, the initial conductivity is repeatably restored with ∼90% efficiency after 15 s healing time, and the mechanical
properties are completely restored after ∼10 min. The composite resistance varies inversely with applied flexion and tactile
forces. These results demonstrate that natural skin’s repeatable self-healing capability can be mimicked in conductive and
piezoresistive materials, thus potentially expanding the scope of applications of current electronic skin systems.

structural safety12, enabling new biological applications18,19, creating

T
he remarkable ability of human skin to self-repair allows it
to function as a protective barrier, despite being subjected to
constant damage, while continuously sensing the external
environment. An ideal biomimetic electronic sensor skin should
demonstrate similar mechanical sensing and repeatable self-
healing capabilities, the fulfillment of which will simultaneously
require self-healing electrodes (conductivity .1 S cm21) and
tactile sensors. For practical use, both electrodes and sensors must
further demonstrate repeatable electrical and mechanical healing
at room temperature, even at the same damage location, much
like human skin. Electronic skins are approaching human skin-
like properties and performance in terms of mechanical sensing
and form factor1–9, but the ability to repeatably self-heal has not
been demonstrated in electronic skins so far. Such ambient repeata-
ble self-healing and mechanical-sensing capability will be useful in
bioprosthetics and the emerging field of soft robotics10,11, where
robots are made entirely of soft, flexible and conformable materials.
In recent years there has been intense research into self-healing
materials, but this has largely focused on designing unique stimu-
lus-responsive polymer systems for the restoration of mechanical
properties. Chen and colleagues used thermally reversible Diels–
Alder reactions with dynamic covalent bonds to create a tough
epoxy-like polymer that can structurally heal when heat-treated
above 120 8C (ref. 12), whereas Burnworth and colleagues showed
that a metallo-supramolecular polymer can be selectively healed
by converting an optical stimulus to localized heat13. Recently,
Leibler and co-workers pioneered a repeatably healable thermo-
plastic elastomer material based on the use of supramolecular inter-
actions for spontaneous healing14,15. In the area of fault-tolerant soft
electronics, Yuan and colleagues first demonstrated the use of
high-strain-capable carbon-nanotube electrodes that can selectively
combust or ‘self-clear’ in localized short circuits to maintain con-
stant operation of the dielectric elastomer actuators16,17. These
smart material systems are tremendously useful for enhancing
long-lived super-hydrophobic coatings20,21, increasing the lifespan
of materials and improving environmental sustainability12,16,22.
In spite of the great promise these systems provide, there is one
striking omission in their properties—a lack of high bulk electrical
conductivity in the self-healing materials. This shortcoming limits
their potential use in electronic applications. Bielawski and col-
leagues proposed the use of organometallic polymer thin films
as self-healing conductors, but these demonstrated very low conduc-
tivities (1023 S cm21) and required high temperatures and organic
solvents for cracks to be healed23. White, Moore and co-workers pio-
neered the use of microcapsules containing various types of liquid-
precursor healing agents for structural healing24,25, and have recently
used capsules filled with various conductive agents or solvents for
autonomous electrical healing of thin metal films26,27. In these
systems, the local healing agent is depleted after capsule rupture,
having actioned just a single local healing event28. In addition,
these conductive healing agents do not allow simultaneous struc-
tural healing. To impart conductive healing to thin films, Li and col-
leagues recently used water as the self-healing agent29. However, the
use of potentially volatile plasticizers as additives or healing agents is
undesirable in electronic systems because of the risk of contami-
nation or electronic short circuits arising from escaped additives.
Furthermore, no self-healing tactile sensors have been reported30,31.
Clearly, combining repeatable self-healing, force sensitivity and high
bulk electrical conductivity remains a challenge.
Here, we show the first repeatable, room-temperature self-
healing electronic sensor skin, using a supramolecular organic–
inorganic composite. A conductivity as high as 40 S cm21 was
measured for our composite, which is four orders of magnitude
higher than previously reported self-healing conductive organome-
tallic polymer films23. The composite material is mechanically flex-
ible, and is capable of sensing tactile and flexion forces. Although
there has been substantial research into conductive polymer

1
Department of Electrical Engineering, Stanford University, David Packard Building, Stanford, California 94305, USA, 2 Department of Chemical Engineering,
Stanford University, 381 North–South Mall, Stanford, California 94305, USA. † These authors contributed equally to this work. *e-mail: zbao@stanford.edu

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© 2012 Macmillan Publishers Limited. All rights reserved.

ARTICLES NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192

a b

C6H13 H H
H H
N N N N
7 N
H
O
O
C8H15 H H
7

N N

O O
O

C6H13
7

H15C8 Nanostructured
O µNi particle

7
H H
H13C6 N N
N
7

H
O

Urea

Heat

Figure 1 | Preparation of the self-healing composite. a, Proposed interaction of oligomer chains with mNi particles. Pink lines, linear and branched polymers
form the randomly branched network; blue and purple shapes, urea groups at the ends of the branched polymers form the primary hydrogen bonds between
the polymer chains. b, SEM of the wetting of the oligomer on the preserved nano-corrugated surface of the mNi particles. Scale bar, 1 mm. c, Manufacturing
process flow. Left: an initial randomly branched oligomer network in chloroform is synthesized from Empol 1016 and diethylenetriamine (DETA). Middle: mNi
particles are mixed in to form a homogeneous suspension of the oligomer network. Right: optical image of the compression-moulded self-healing electronic
composite material, demonstrating the flexibility of the material. Scale bar, 1 mm.

composites, this is the first demonstration of a self-healing conduc-
tive composite made using a supramolecular polymer host.
Materials fabrication
Figure 1 presents a schematic of material preparation. Our material
consists of two components: (i) a supramolecular polymeric hydro-
gen-bonding network with a glass transition temperature Tg below
room temperature and (ii) chemically compatible micro-nickel
(mNi) particles with nanoscale surface features (Fig. 1a). The supra-
molecular polymeric hydrogen-bonding network provides the self-
healing function via the large number of weak hydrogen bonds,
which break preferentially (instead of the stronger covalent bonds)
during a mechanical damage event. These ‘broken’ hydrogen
bonds have been shown to dynamically associate and dissociate at
room temperature to provide a passive healing mechanism at
the fracture surface14,15,32–35. Additionally, a low Tg enables the

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NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192
polymer chains on fractured interfaces to rearrange, wet and
diffuse36, thereby allowing healing under ambient temperatures. A
low Tg alone, without hydrogen-bonding sites, does not allow self-
healing. For example, polydimethoxysilane (PDMS) has a Tg of
,2100 8C, but due to the lack of reversible polymer bonding,
PDMS composite systems cannot self-heal.
A mixing process that preserves the nanofeatures of the mNi par-
ticles (Fig. 1b) was used (see Methods) to disperse the mNi particles
into the polymer network, followed by thermal crosslinking with
urea (Fig. 1c). mNi particles disperse well in the supramolecular
hydrogen-bonding network for two reasons. First, the relatively
large size of the spherical particles leads to a reduction in phase
aggregation, while the nanometre-scale corrugated surface provides
an adequate surface area for wetting. Second, the well-known pres-
ence of a thin native oxide layer on the particles37 provides an affi-
nity for hydrogen bonds in our synthesized supramolecular
oligomers. The presence of reversible hydrogen bonding allows
the composite material to self-adhere (without the use of adhesives)
to flexible substrates such as oxygen plasma-activated polyethylene
terephthalate (PET) sheets. The laminated composite can withstand
flexing into various conformations (Supplementary Fig. S1). The
composite material can be as thin as 600 mm, a limit currently set
by the compression moulding set-up.
Electrical characterization of self-healing composite
Figure 2a shows the composite cross-section morphology with
increasing nickel volume fraction, obtained using scanning electron
microscopy (SEM) analysis. No phase aggregation of nickel particles
was observed up to 31% volume fraction (75 wt%) of mNi particles.
To further assess the dispersion of the nickel particles, the variation
of resistance within each sample was measured. The resistance was
found to be linearly proportional to the distance between the probes
(Supplementary Fig. S2), implying good dispersion and a lack of
phase aggregation of nickel particles in the supramolecular host.
The conductivities of each composite were measured using a four-
point probe technique. Six samples for each volume fraction (total
54 samples) were measured, and the average volume conductivities
are plotted with error bars (standard deviation) in Fig. 2b. At 31%
volume fraction, the conductivity reached 40 S cm21 (average
18 S cm21), making this composite suitable for use in electrodes
in electronic devices38. The nanostructures on the surface of the
nickel microparticles are essential for imparting high conductivity,
because they facilitate interparticle quantum tunnelling by enhan-
cing the local electric field at the asperities of the surface41. As
shown in Fig. 2b, the conductivity of the composite with smooth
nickel microparticles remained below 1 × 1026 S cm21, even at
high loading (Supplementary Fig. S3).
The trend of an increase in volume conductivity as a function of
nickel volume ratio agrees well with percolation theory39, which
describes an exponential increase above the percolation threshold
(solid red line in Fig. 2b; for derivation see Supplementary
Fig. S4). The percolation threshold was found to be 0.15 volume
fraction of the mNi particles, which is close to the ideal percolation
threshold value of 0.16 for spherical particles. Below the percola-
tion threshold, the conductivities were considerably lower and rela-
tively constant, which also agrees with percolation theory40.
The composite material displayed the typical linear, non-hysteretic
current–voltage characteristics expected of a good electrical conductor
(Supplementary Fig. S5). Figure 2c shows that the conductive compo-
site can be used in conducting wires in an electronic circuit for devices
such as light-emitting diodes (LEDs). A turn-on resistance of 200 V
was observed, as indicated by the linear region of the current–voltage
curve (due to parasitic resistance from two thin 50-mm-diameter stain-
less steel wires used as the flexible leads to the voltage source meter).
To investigate electrical healing, the conductor was completely
bifurcated using a scalpel and the two fractured surfaces brought
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ARTICLES
together. Figure 2d describes the time evolution of a typical electrical
healing process. An open circuit was formed following complete
severance of the self-healing conductor. As the edges of the compo-
site were brought into contact, the conductivity increased and the
resistance dropped to several kilo-ohms. At this stage, the opposite
halves of the bifurcated samples were not self-supporting. However,
when a gentle pressure was applied for a duration of 15 s, the con-
ductivity returned to close to its initial value, and the composite
became self-supporting. At release, a very slight increase in resist-
ance was observed initially. This increase can be explained by the
slight viscoelastic nature of the composite, which slightly increased
the conduction path distance. However, as the healing progressed,
the resistance gradually decreased. As electrical conductivity is
determined by the proximity of the filler particle, the re-association
of the hydrogen bonds within the polymer at room temperature
enables high electrical healing efficiencies by allowing the particles
to be closely packed at the healing interface under gentle contact
pressures (50 kPa, similar to the pressure applied to a minor cut
wound on skin; Supplementary Fig. S6).
We can define the conductive healing efficiency term, helec , as
the proportion of conductivity restored relative to the original
conductivity. Figure 2e shows that successive cuts at the same
location were also healed with high helec , demonstrating excellent
repeatable restoration of electrical performance in our self-healing
electronic composite. The duration of contact is an important
factor in determining helec , indicating that mechanical healing is
essential for conductive healing. A 15 s contact resulted in a
nearly full restoration of the electrical properties, with helec reaching
as high as 98% (Supplementary Fig. S7). A battery-powered
circuit was constructed to demonstrate further the potential of
electromechanical self-healing for electronic circuits (Fig. 2f,
Supplementary Movie S1).
Mechanical characterization of self-healing composite
Figure 3a shows that increasing the mNi particle concentration ben-
eficially strengthens the polymer network and increases the Young’s
modulus and maximum tensile stress that the composite can
withstand. Mechanical healing efficiencies can be quantified using
toughness, because this takes into account the restoration of both
stress and strain (area under the stress–strain curve). We define
the mechanical healing efficiency hmech as the proportion of tough-
ness restored relative to the original toughness. Figure 3b shows a
representative stress–strain curves for a 31% nickel volume fraction
composite under different healing conditions. From these curves,
hmech was found to be a function of healing time. The longer the
healing time, the higher the value of hmech , as hydrogen bonds con-
tinue to re-associate with one another between the interfaces
(Fig. 3b). Even at the highest nickel volume fraction of 31%, the
toughness recovery of the composite increased by a factor of three
to 41% after a healing time of 10 min, compared to 13% for
5 min, at room temperature. The partially healed composite broke
at the site of initial fracture, possibly due to remnant defects.
However, full restoration of the toughness was achieved at a gentle
heating temperature of 50 8C for 10 min and the fully healed
sample fractured at a different site upon tensile testing. The tough-
ness recovery was higher than that of the original composite, which
is a phenomenon that has been observed in other supramolecular
self-healing polymer systems13. For superficial damage, such as a
scratch, the scar at the damaged interface could be fully healed
(Fig. 3c) after 5 min at 50 8C.
Supplementary Fig. S8 presents a comparison of the mechanical
healing efficiencies of a different nickel volume fraction using three
samples at each composition. As the nickel particle concentration
increased, hmech decreased, because part of the surface area of the
fractured interface was now occupied by nickel particles. Both
mechanical and electrical healing were also negatively affected if
827
ARTICLES NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192

a 75% μNi b 102

Nanostructured μNi
101 Smooth spherical Ni particles
Percolation theory fit
100

10−1

Conductivity (S cm−1)
10−2

Increasing conductivity
50% μNi 1 μm
10−3

10−4

10−5

10−6 1 μm

30% μNi 10−7

10−8

10−9
0.05 0.10 0.15 0.20 0.25 0.30
Ni volume fraction

c d
3.5
Cut
3.0 109

2.5
107
Resistance (Ω)
Current (mA)

2.0
105
1.5
Contact
1.0 103
Pressed Released
0.5
101
0.0

−0.5 10−1
−1 0 1 2 3 0 20 40 60 80 100
Voltage (V) Time (s)

e 109 f
1st cut 2nd cut 3rd cut
107
Resistance (Ω)

105
1 2

103

101

10−1 3 4
0 200 400 600 800 1,000 1,200 1,400 1,600
Time (s)

Figure 2 | Electrical and conductive healing efficiency characterization of self-healing composite. a, Cross-sectional SEM images of composite materials
showing decreasing particle separation distance as mNi concentration increases. No aggregation was observed even at a high mNi loading of 31 vol% (75 wt%).
Scale bar, 20 mm for all images. b, Volume electrical conductivity as a function of mNi particle concentration from four-point probe measurements. Error bars
represent standard deviation from six samples per volume fraction (Supplementary Table S2). Inset: SEM images of the nanoflower-like surface of the mNi
(top) and the comparatively smooth surface of comparison spherical nickel particles (bottom). The microparticles (as from the manufacturer) have a small
size distribution around a diameter of 2–5 mm. Red line represents the best-fit line for conductivity above percolation threshold using percolation theory
(Supplementary Fig. S4). c, Current–voltage curve of a commercial LED using self-healing electrically conductive composite wire moulded into an ‘S’ shape.
Inset: image of circuit taken at 2.5 V (scale bar, 10 mm). d, Time evolution of the electrical healing process using resistance measurements for 15 s healing
time at room temperature. e, Repeated electrical healing for three cuts at the same severed location. f, Demonstration of the healing process for a conductive
composite with an LED in series with a self-healing electrical conductor. 1, undamaged conductor; 2, completely severed conductor (open circuit); 3, electrical
healing (inset shows conductor being self-supporting); 4, healed film being flexed to show its mechanical strength and flexibility after only 5 min at room
temperature (Supplementary Movie S1).

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NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192
a b
15 vol% µNi
100 23 vol% µNi
31 vol% µNi
Tensile stress (MPa)
Tensile stress (MPa)
10−1
10−2
0 20 40 60 80 100
Strain (%)
Figure 3 | Mechanical and healing efficiency characterization of the self-healing composite. a, Tensile measurements of composites with different nickel
volume ratios. b, Typical stress–strain curves of original and healed samples for different healing times and temperature for 31 vol% mNi composite. RT, room
temperature. c, Optical microscope image of damaged sample and complete scar healing for 31 vol% mNi composite. Scale bar, 1 mm.
the interfaces were left in ambient air for over 2 min
(Supplementary Fig. S9). This can be attributed to a loss of hydro-
gen-bonding ability due to absorption of moisture from the ambient
air14. This suggests that hydrogen bonding is essential for the self-
healing mechanism.
To further study the effect of hydrogen-bonding density on
electrical and mechanical healing, a control polymer, composite A,
was synthesized to have similar mechanical properties and Tg , but
significantly fewer hydrogen-bonding sites (Supplementary
Fig. S10). This was achieved by using oxalyl chloride instead of
urea, followed by loading the polymer with nanostructured mNi
particles to obtain similar electrical conductivities. Composite A elec-
trically healed to only 7% of its original value, whereas the original
polymer composite healed to 90%, indicating the importance of
proper tuning of the number of hydrogen-bonding sites and strength.
We also synthesized another control polymer, composite B, in which
the hydrogen-bonding density was lowered by decreasing the
amount of urea (Supplementary Fig. S11). Composite B demon-
strated reduced mechanical and electrical healing efficiencies,
further indicating that hydrogen bonding was driving the healing.
If there is no mechanical healing at the interface, the conductivity
between the fractured pieces will not be effectively restored once
the pressure is released. For example, when a polymer such as
PDMS without hydrogen bonding was used, electrical and mechan-
ical self-healing were not observed (Supplementary Fig. S12).
Self-healing composite as electronic skin
Using lower mNi concentrations, with the particles spaced further
apart, we realized self-healing piezoresistive sensors. The larger
particle spacing allows a more significant change in resistance as
the compressive forces bring the mNi particles closer within the
polymer matrix. Such behaviour has been observed with other
non-self-healing composite systems, but here we apply it to a supra-
molecular composite with dynamic healing. At mNi concentrations
near the percolation threshold (15 vol%), the composite material
can be used to sense mechanical forces such as a flexion (Fig. 4a)
and a tactile pressure (Fig. 4b). When the composite material was
flexed, compressive stresses built up at the inner curvature. The
mNi particles therefore approached closer to one another and
thereby reduced the composite’s resistance. The greater the flexion
angle u (defined in Fig. 4a), the lower the resistance. The change
in resistance was repeatable both in forward (increasing u) and
reverse (decreasing u) directions. Electronic skins are often fabri-
cated by mounting sensors or circuitry on flexible substrates such
as PET sheets. Our sensor was mounted on 50-mm-thick PET
and a similar trend in response was found. The slight differences
can be attributed to the different deformation modes taking place
on a free-standing film versus a mounted film—in the case of a
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ARTICLES
c
100
x
x xx
10−1
Original
2 min RT
5 min RT
10 min RT
5 min 50 °C
10−2
0 10 20 30 40 Damaged Healed
Strain (%)
free-standing film, one side is compressed but the other side
is stretched.
Similarly, a tactile sensor could be completely constructed from
our self-healing materials by using a parallel-plate structure with
the piezoresistive composite sandwiched between layers of the con-
ductive composite. The piezoresistive response of this arrangement
is shown in Fig. 4b. The increase in conductivity is exponentially
dependent on stress, similar to other piezoresistive sensors based
on carbon black42. Although such dynamically healing polymer
systems typically suffer from a viscoelastic effect (creep), which
affects the time response to mechanical forces, the addition of
nickel particles significantly reduces the viscous modulus, and the
piezoresistive sensors can track mechanical loads without showing
significant relaxation times, as shown by the tracking of various
ramped loads in Supplementary Fig. S13. The flexion and tactile
sensors were then characterized at temperatures up to 40 8C
(Supplementary Fig. S14). The sensitivities increased as a result of
thermal expansion and slight decrease in modulus at elevated
temperatures.
As a step towards achieving the goal of using our self-healing
composite as electronic skin, we integrated the tactile and flexion
sensors into a humanoid mannequin (Fig. 4c). The sensors were
located on the palm and elbow joint in the path of electric circuits,
using LEDs as indicators of mechanical forces. We demonstrated the
ability to detect varying pressures and changes in the positions of
the limbs (proprioception; Fig. 4d,e, Supplementary Movie S2).
The sensors modulated current flow through the sensor circuit by
means of changes in their resistance depending on pressure and
flexion angle of the limb. This in turn changed the intensity of
the respective LEDs depending on the pressure and flexion angle.
The flexibility of the material is clearly advantageous for detecting
the position of movable joints.
Conclusions
In summary, we have demonstrated the first ambient repeatable
self-healing electronic composite material that can be used to
sense mechanical forces. Although the Tg of the polymer is
–20 8C, the addition of nanostructured mNi particles with nano-
structured surfaces significantly enhances the mechanical properties
and raises the Tg to 10 8C (Supplementary Fig. S15). Furthermore,
mNi-composite samples have healing efficiencies that decrease
with surface exposure time, indicative that healing is driven by
hydrogen bonding re-association between the cut surfaces.
Although the Tg of the composite sets the lower bound of the oper-
ating temperature range for efficient healing, as the polymer chains
are less mobile at or below Tg , this potential limitation can be
overcome by tuning the mechanical properties of the supramole-
cular binder by controlling its crosslinking density and/or using
829
ARTICLES NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192

a b
1.0 Free-standing forward
Free-standing backward
Self-adhered PET forward
Self-adhered on PET backward
104
Relative resistance change

0.8

Resistance (Ω)
0.6
103

0.4
Force y = 104.7−6.6x
y = 1.0 − 0.01θ
θ
102 Self-healing Self-healing
0.2 conductor tactile sensor

y = 1.0 − 0.03θ + 2 × 10−4θ2

0.0
0 10 20 30 40 50 60 70 80 0.0 0.1 0.2 0.3 0.4
Flexion angle θ (deg) Pressure (MPa)

c d
3V
V

Self-healing
conductor

V 3V
LED

Self-healing
flexion
sensor
Self-healing
tactile
sensor

Relaxed Flexed
e

No pressure ~50 kPa ~1 MPa ~2 MPa

Figure 4 | Characterization and application of the self-healing electronic sensor skin. a, Flexion sensor electrical response in both free-standing and
self-adhered modes on 50-mm-thick PET substrates. Inset: definition of flexion angle u. Equation represents least-squares fit (dotted line) relationship of
resistance and flexion angle. b, Tactile sensor response at increasing peak pressure values (inset: sensor schematic). Equation represents least-squares fit
relationship (dotted line) of resistance and applied pressure. c, Self-healing flexion and tactile sensor circuit schematic and mounting on a fully articulated
wooden mannequin. See Supplementary Movie S2 for a real-time demonstration. A flexion sensor was mounted on the inner elbow region. A tactile sensor
was mounted on the palm. LEDs (centre of body and eye region) are used to transduce the mechanical deformation into visible analogue light-intensity
outputs. d, Flexion sensor circuit demonstration: LED ‘eyes’ light up after the elbow is bent. The intensity increases with increasing elbow flexion. e, Tactile
sensor circuit demonstration. LED intensity responds as a function of increasing tactile pressure.

multiple composite materials tuned to a different temperature functional lifespan of the skin. Because they are electrically conduct-
operating range. ing, we can also effectively detect a severe damage event through a
Our self-healing composite is the first bulk conductive composite change in electrical resistance, and repair the skin by simply con-
that has an organic supramolecular polymer as host and inorganic tacting the fractured interfaces. The self-healing electronic skin
metal particles with nanostructured morphology as fillers. The demonstrated here represents just one possible sensing functionality
rate of electrical healing is rapid (within 15 s). These functional achievable with this supramolecular polymer system. We anticipate
self-healing electronic sensor skins potentially enhance the that other self-healing polymer systems might also benefit from such

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NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192
a functional composite strategy to enable new electronic functional-
ities. We foresee that our bottom-up strategy of synergizing
supramolecular interactions43 with carefully selected chemically
compatible nano-inorganic fillers with desired electronic properties
may enable a future class of functional, self-healing electronic
devices ranging from passive resistors and capacitors to electro-
active sensor devices such as semiconductors, solar cells and artifi-
cial soft actuators17,44.
Methods
Composite manufacture. The synthesis of our supramolecular hydrogen-bonding
network was modified from the work of Leibler and colleagues to enable plasticizer-
free synthesis by deliberately lowering the density of hydrogen bonding to obtain
a supramolecular hydrogen bonding network with Tg , 0 8C (Supplementary
Fig. S15). A mixture of 41.5 g Empol 1016 (donated by Congnis, 80 wt% diacids,
16 wt% triacids, Supplementary Fig. S16) and 17 g diethylenetriamine (DETA,
Sigma Aldrich) was stirred continuously at 160 8C for 24 h under an argon
atmosphere. The product was then dissolved in 150 ml chloroform followed by
washing with 150 ml water and 75 ml methanol, and vacuum removal of
chloroform. The oligomer was dissolved in 1 ml of chloroform and then mixed with
mNi particles (Novamet) using a Dual Asymmetric Centrifugal Mixer (Flacktek)
(3,500 r.p.m., 135 s) to obtain a homogeneous suspension. The suspension was then
reacted with 300 mg urea (Sigma Aldrich) at 135 8C under constant mechanical
stirring. The reaction time between the initial randomly branched oligomer and urea
was strictly controlled at 40 min, such that only the primary amines were
converted into carbamide groups (Supplementary Fig. S16). (Beyond 40 min,
the composite material became brittle and inflexible.) The product was then
compression-moulded (100 8C) to 1.5-mm-thick sheets using Teflon moulds.
Although the polymer hydrogen-bonding network does not hold its shape, the
addition of mNi strongly enhances the mechanical properties tremendously, as
demonstrated by the increased Tg (Supplementary Fig. S14) and rheological
measurements (Supplementary Figs S17–S19). In contrast, carbon black composites
do not show any increase in Tg at all volume ratios due to the lack of a strong
interaction with the polymer matrix. Furthermore, multiwalled carbon nanotube
(MWNT)-based composites demonstrated poor electrical performance, despite their
high intrinsic conductivity, due to severe bundling of the MWNTs in our
polymer host.
Synthesis of control composite A. The randomly branched oligomer (M-NH2 ,
1.5 g) was dissolved in 3 ml of dichloromethane and 0.3 ml of triethylamine was
added. Oxalyl chloride (1 mmol) was then added to the mixture, dropwise, under
vigorous stirring. After reaction for a further period of 1 h, the dispersion was
mixed with nickel particles. The resulting slurry was heated at 135 8C for 10 min to
remove all solvents, followed by compression moulding into samples
for characterization.
Synthesis of control composite B. The synthesis is similar to that for self-healing
composite A, but the urea content was reduced to 50 mg for every 1.5 g of M-NH2.
Mechanical testing. Mechanical tensile-stress experiments were performed using an
Instron 5848 Microtester according to ASTM D638 normalized samples. We tested
three samples for each volume fraction. Tensile experiments were performed at room
temperature (25 8C) at a strain rate of 1 mm min21. Healing experiments were
performed at room temperature by bringing severed samples together and pressing
with a hand pressure of 50 kPa. Rheological experiments were carried out using a
stress-controlled rheometer (TA Instruments Model AR-G2) with a parallel plate
attachment (40 mm). The gap was at least 110 mm for each sample. Oscillatory
experiments were carried out with the frequency varied from 0.01 to 10 Hz while
maintaining the strain at 1%. Frequency sweeps from 0.1 to 1 Hz at 0.1% strain were
performed at temperatures between 30 and 0 8C. Increments of 2 8C were used with
1 min equilibration.
Electrical testing. Current–voltage measurements were performed using a Keithley
2400 source meter. All conductivity measurements were performed on 3-mm-thick
samples cut to 5 mm × 15 mm, using four-point probe measurements. Two-point
probes were used to measure resistance variation across samples (Supplementary
Fig. S2). For low-conductivity samples below the percolation threshold, the
resistance was obtained using an Agilent E4980A Precision LCR meter. Samples
were connected with patterned flexible copper-clad polyimide films (thickness,
12 mm; Dupont). Tactile sensor cycling measurements were performed on a
mechanized z-axis stage (Newmark Systems, 0.1 mm resolution), and a force gauge
(Mark 10) was used to apply loads to the sensor pads on a custom-built probe
station. Photographic images of increasing LED intensity were taken at the same
aperture and exposure settings.
Received 11 June 2012; accepted 1 October 2012;
published online 11 November 2012
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© 2012 Macmillan Publishers Limited. All rights reserved.
ARTICLES
References
1. Kim, D. H. et al. Epidermal electronics. Science 333, 838–843 (2011).
2. Mannsfeld, S. C. B. et al. Highly sensitive flexible pressure sensors with
microstructured rubber dielectric layers. Nature Mater. 9, 859–864 (2010).
3. Takei, K. et al. Nanowire active-matrix circuitry for low-voltage macroscale
artificial skin. Nature Mater. 9, 821–826 (2010).
4. Wagner, S. et al. Electronic skin: architecture and components. Physica E 25,
326–334 (2004).
5. Cotton, D., Graz, I. & Lacour, S. P. A multifunctional capacitive sensor for
stretchable electronic skins. Sensors J. 9, 2008–2009 (2009).
6. Lipomi, D. J. et al. Skin-like pressure and strain sensors based on transparent
elastic films of carbon nanotubes. Nature Nanotech. 6, 788–792 (2011).
7. Someya, T. et al. A large-area, flexible pressure sensor matrix with organic
field-effect transistors for artificial skin applications. Proc. Natl Acad. Sci. USA
101, 9966–9970 (2004).
8. Ramuz, M., Tee, B. C.-K., Tok, J. B-H. & Bao, Z. Transparent, optical, pressure-
sensitive artificial skin for large-area stretchable electronics. Adv. Mater. 24,
3223–3227 (2012).
9. Pang, C. et al. A flexible and highly sensitive strain-gauge sensor using reversible
interlocking of nanofibres. Nature Mater. 11, 795–801 (2012).
10. Ilievski, F., Mazzeo, A., Shepherd, R., Chen, X. & Whitesides, G. M. Soft robotics
for chemists. Angew. Chem. Int. Ed. 50, 1930–1935 (2011).
11. Shepherd, R. F. et al. Multigait soft robot. Proc. Natl Acad. Sci. USA 108,
20400–20403 (2011).
12. Chen, X. et al. A thermally re-mendable cross-linked polymeric material.
Science 295, 1698–1701 (2002).
13. Burnworth, M. et al. Optically healable supramolecular polymers. Nature 472,
334–337 (2011).
14. Cordier, P., Tournilhac, F., Soulié-Ziakovic, C. & Leibler, L. Self-healing and
thermoreversible rubber from supramolecular assembly. Nature 451,
977–980 (2008).
15. Montarnal, D., Tournilhac, F., Hidalgo, M., Couturier, J-L. & Leibler, L. Versatile
one-pot synthesis of supramolecular plastics and self-healing rubbers. J. Am.
Chem. Soc. 131, 7966–7967 (2009).
16. Yuan, W. et al. Fault-tolerant dielectric elastomer actuators using single-walled
carbon nanotube electrodes. Adv. Mater. 20, 621–625 (2008).
17. Brochu, P. & Pei, Q. Advances in dielectric elastomers for actuators and artificial
muscles. Macromol. Rapid Commun. 31, 10–36 (2010).
18. Nakahata, M., Takashima, Y., Yamaguchi, H. & Harada, A. Redox-responsive
self-healing materials formed from host–guest polymers. Nature Commun. 2,
511–516 (2011).
19. Phadke, A. et al. Rapid self-healing hydrogels. Proc. Natl Acad. Sci. USA 109,
4383–4388 (2012).
20. Li, Y., Li, L. & Sun, J. Bioinspired self-healing superhydrophobic coatings.
Angew. Chem. Int. Ed. 122, 6265–6269 (2010).
21. Wong, T-S. et al. Bioinspired self-repairing slippery surfaces with pressure-
stable omniphobicity. Nature 477, 443–447 (2011).
22. Wang, Q. et al. High-water-content mouldable hydrogels by mixing clay and a
dendritic molecular binder. Nature 463, 339–343 (2010).
23. Williams, K., Boydston, A. & Bielawski, C. Towards electrically conductive,
self-healing materials. J. R. Soc. Interface 4, 359–362 (2007).
24. White, S. R. et al. Autonomic healing of polymer composites. Nature 409,
794–797 (2001).
25. Odom, S. A. et al. Restoration of conductivity with TTF-TCNQ charge-transfer
salts. Adv. Funct. Mater. 20, 1721–1727 (2010).
26. Blaiszik, B. J. et al. Autonomic restoration of electrical conductivity. Adv. Mater.
24, 398–401 (2012).
27. Odom, S. A. et al. A self-healing conductive ink. Adv. Mater. 24,
2578–2581 (2012).
28. Blaiszik, B. J. et al. Self-healing polymers and composites. Annu. Rev. Mater. Res.
40, 179–211 (2010).
29. Li, Y., Chen, S., Wu, M. & Sun, J. Polyelectrolyte multilayers impart healability to
highly electrically conductive films. Adv. Mater. 24, 4578–4582 (2012).
30. Ghosh, S. K. Self-Healing Materials: Fundamentals, Design Strategies, and
Applications (Wiley, 2009).
31. Zhang, M. Q. & Rong, M. Z. Self-Healing Polymers and Polymer Composites
(Wiley, 2011).
32. Wojtecki, R. J., Meador, M. A. & Rowan, S. J. Using the dynamic bond to access
macroscopically responsive structurally dynamic polymers. Nature Mater. 10,
14–27 (2010).
33. Brunsveld, L., Folmer, B. J. B., Meijer, E. W. & Sijbesma, R. P. Supramolecular
polymers. Chem. Rev. 101, 4071–4098 (2001).
34. Lehn, J-M. Supramolecular polymer chemistry—scope and perspectives.
Polym. Int. 51, 825–839 (2002).
35. Wang, L. et al. A new approach for the fabrication of an alternating multilayer
film of poly(4-vinylpyridine) and poly(acrylic acid) based on hydrogen bonding.
Macromol. Rapid Commun. 18, 509–514 (1997).
36. Wool, R. Self-healing materials: a review. Soft Matter 4, 400–418 (2008).
831
ARTICLES NATURE NANOTECHNOLOGY DOI: 10.1038/NNANO.2012.192

37. Uchikoshi, T., Sakka, Y., Yoshitake, M. & Yoshihara, K. A study of the
passivating oxide layer on fine nickel particles. Nanostruct. Mater. 4,
199–206 (1994).
38. Sekitani, T. et al. A rubberlike stretchable active matrix using elastic conductors.
Science 321, 1468–1472 (2008).
39. Stauffer, D. & Aharony, A. Introduction to Percolation Theory (Taylor &
Francis, 1994).
40. Nan, C. W., Shen, Y. & Ma, J. Physical properties of composites near percolation.
Annu. Rev. Mater. Res. 40, 131–151 (2010).
41. Bloor, D., Graham, A., Williams, E. J., Laughlin, P. J. & Lussey, D. Metal–
polymer composite with nanostructured filler particles and amplified physical
properties. Appl. Phys. Lett. 88, 102103 (2006).
42. Wang, P. & Ding, T. Conductivity and piezoresistivity of conductive carbon
black filled polymer composite. J. Appl. Polym. Sci. 116, 2035–2039 (2010).
43. Stoddart, J. F. Thither supramolecular chemistry? Nature Chem. 1, 14–15 (2009).
44. Carpi, F., Bauer, S. & De Rossi, D. Stretching dielectric elastomer performance.
Science 330, 1759–1761 (2010).
Acknowledgements
The authors acknowledge funding support from the Air Force Office of Scientific Research
(grant no. FA9550-12-1-01906). B.C-K.T. acknowledges support from the National Science
Scholarship (NSS) from the Agency for Science, Technology and Research (A*STAR). R.A.
acknowledges support from the Stanford Graduate Fellowship (SGF) and the Center for
Advanced Molecular Photovoltaics (CAMP). Z.B. acknowledges support from LG Display.
The authors thank D.J. Lipomi and J. Mei for fruitful discussions, and J.B-H. Tok, N. Liu
and Y. Tan for proofreading the manuscript drafts. Thanks also go to I. Wong and
Y. Ohkura for help with mechanical testing, and to Y. Diao for initial help with
material characterization.
Author contributions
B.C-K.T., C.W. and Z.B. conceived, designed and directed the project. B.C-K.T., C.W.
and R.A. performed the experiments. C.W. synthesized and characterized the polymer
materials. R.A. performed all the rheological measurements and analysis. B.C-K.T.
and C.W. co-wrote the manuscript draft. All authors discussed the results and commented
on the manuscript.
Additional information
Supplementary information is available in the online version of the paper. Reprints and
permission information is available online at http://www.nature.com/reprints. Correspondence
and requests for materials should be addressed to Z.B.
Competing financial interests
The authors declare no competing financial interests.

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