ARTICLE

Received 3 Dec 2015 | Accepted 27 May 2016 | Published 29 Jun 2016 DOI: 10.1038/ncomms12078 OPEN

Magnetic assembly of transparent and conducting

graphene-based functional composites
Hortense Le Ferrand1, Sreenath Bolisetty2, Ahmet F. Demirors1, Rafael Libanori1, Andre R. Studart1
& Raffaele Mezzenga2

Innovative methods producing transparent and exible electrodes are highly sought in
modern optoelectronic applications to replace metal oxides, but available solutions suffer
from drawbacks such as brittleness, unaffordability and inadequate processability. Here we
propose a general, simple strategy to produce hierarchical composites of functionalized
graphene in polymeric matrices, exhibiting transparency and electron conductivity. These are
obtained through protein-assisted functionalization of graphene with magnetic nanoparticles,
followed by magnetic-directed assembly of the graphene within polymeric matrices
undergoing solgel transitions. By applying rotating magnetic elds or magnetic moulds, both
graphene orientation and distribution can be controlled within the composite. Importantly, by
using magnetic virtual moulds of predened meshes, graphene assembly is directed into
double-percolating networks, reducing the percolation threshold and enabling combined
optical transparency and electrical conductivity not accessible in single-network materials.
The resulting composites open new possibilities on the quest of transparent electrodes for
photovoltaics, organic light-emitting diodes and stretchable optoelectronic devices.

1 Complex Materials, Department of Materials, ETH Zurich, Zurich 8093, Switzerland. 2 Food and Soft Materials, Department of Health Sciences and Technologies,

ETH Zurich, Zurich 8092, Switzerland. Correspondence and requests for materials should be addressed to A.R.S. (email: [email protected]) or to R.M.
(email: [email protected]).

NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications 1

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078

printing combined with thermal treatment29 or chemical

T
he increasing demand for optoelectronic tools from
tissue-compatible biomedical devices for health monitoring vapour deposition followed by etching30,31, the fabrication costs
to indiumtin-oxide-free electrodes for exible solar associated with these techniques greatly reduce their potential for
cells has recently stimulated the search for cost-effective materials large-scale applications and call for new strategies.
with comparable performance, but improved exibility to One enticing approach to further decrease the amount of
replace the commonly used stiff and brittle components14. conductive particles needed to achieve the percolation threshold
There is an extensive library of existing potential materials is to fabricate hierarchical composites exhibiting multiple
combining electrical conductivity and transparency, mostly based percolating networks at different length scales32,33. While the
on substrate lms coated with a mesh of nanocarbons or metal potential of this approach has already been demonstrated for
nanowires5,6. These materials present high electrical conductivity, carbon nanotube-based composites34, translation of such
corresponding to a sheet resistance down to 128 Ohm sq  1 with concepts into industrially relevant processes requires simple and
95% transparency, while exibility is provided to a certain extent cost-effective strategies that allow for a deliberate control over the
by the polymeric substrate. However, bulk materials containing spatial distribution of the secondary network. Furthermore,
mixtures of the conductive elements and the exible matrix combination of multiple percolation networks with sufcient
present the advantage to provide more mechanical integrity over optical transparency remains yet to be demonstrated.
sandwich or layered structures, as well as the possibility to create In this study, we describe a simple processing route to fabricate
more complex three-dimensional (3D) circuits. In addition, direct transparent and conducting polymer-based composite lms using
ink writing or 3D printing techniques can be applied to build external magnetic elds to assemble magnetized graphene akes
on-demand materials with inks containing both the transparent into hierarchical networks of predened features. Using
support and the conductive elements79. Conductive and virtual magnetic moulds, transparency is obtained by locally
transparent polymers and blends based on poly(3,4-ethylene- concentrating the dark conductive akes into continuous
dioxythiophene) doped with polystyrene sulfonic acid networks. When large micrometric mesh sizes are used as
(PEDOT:PSS) can reach transparency up to 87% combined moulds, such control is achieved over areas spanning over
with a conductivity of 1.35 S cm  1 for lms of 1 mm thickness10. several centimeters, resulting in double-percolating hierarchical
Yet, even in this case, good performances are typically recorded networks. In addition to spatial control, tuning the orientation of
for ultrathin lms and based on the intrinsic conductivity of its the functionalized graphene akes within the microscopic
constituents. Polymer composites, on the other hand, are pattern further enhances the electrical conductivity. By carefully
attractive alternatives since the insulating polymeric matrix can engineering the mesh size of virtual magnetic moulds, we
be highly exible and optically transparent, whereas the electrical demonstrate how this new strategy can lead to transparent,
properties can be manipulated by controlling the architecture electrically conducting polymergraphene composites with great
of conductive inclusions. The performance of the composite is potential for applications in advanced compliant optoelectronics.
then uniquely based not only on the intrinsic properties of
its constituents but also on the arrangement of the conducting
ller particles within the matrix and the contact between them. Results
Although most physical properties of composite materials Synthesis and processing strategy. Hydrophilic magnetically
are generally enhanced by increasing the ller content, optical responsive reduced graphene oxide (m-rGO) akes are
transparency tends to be reduced due to the difference in synthesized through decoration of exfoliated micrometric
refractive index between ller particles and matrix. Thus, graphene oxide nanosheets (GO) with 10 nm superparamagnetic
new approaches to fabricate exible composite materials iron oxide nanoparticles (SPIONs; (Fig. 1ac)). The attachment
displaying both enhanced electrical conductivity and high of SPIONs is assisted by a multidomain protein, bovine serum
optical transparency must be developed to full the current albumin (BSA), which maintains the magnetic nanoparticles
requirements of optoelectronic applications. adsorbed on the ake surface throughout all the preparation
Recent efforts have focused on employing conductive steps. The physical adsorption of the BSA generates a predened
anisotropic particles exhibiting high aspect ratio to reduce the molecular coating that settles the saturation limit to the number
amount of opaque material needed to reach the percolation of adsorbed molecules and provides more available sites for the
threshold in the composite1115. Elongated allotropes of adsorption of SPIONs. After partial reduction by BSA, a
carbon such as multi- or single-wall carbon nanotubes have treatment with hydrazine at 80 C converts the GO into
been used to yield electrical conductivity corresponding to a reduced graphene oxide (rGO)35 (see Supplementary Fig. 1 and
sheet resistance down to 290 Ohm sq  1 in cellulose nanobrils Supplementary Discussion for details about reduction). If
aerogel membranes while maintaining 90% in transparency and suspended in a liquid, the prepared m-rGO akes exhibit
5% in strain at rupture16 or 34 Ohm sq  1 in 81% transparent high magnetic response, similar to the ultrahigh magnetic
polyethylene terephthalate-congo red single-wall carbon behaviour observed for other anisotropic particles decorated
nanotube composites17. Graphene nanosheets are particularly with SPIONs36. Remarkably, in contrast with the hydrophobic
promising in view of their unique mechanical and electronic nature of rGO, the presence of polar organic groups in the
properties1821 and their availability through well-established surface-adsorbed SPIONs and BSA enables the successful
exfoliation methods2226. Nevertheless, even the remarkable dispersion of the m-rGO akes in polar solvents, preventing the
percolation thresholds typically achieved in graphene-based formation of possible defects associated with graphitic
composites are not low enough to yield materials with aggregation, clustering or deterioration of the matrix during
acceptable optical transparency and colour neutrality27. The post-reduction treatments37,38. We therefore take an advantage of
use of the more processable graphene oxide may partially this unusual hydrophilicity of the m-rGO akes to incorporate
improve this scenario, yet reducing the conductivity, with them into two exemplary commonly used hydrogels, namely
the fate of the nal materials optoelectronic properties still gelatin from bovine skin and poly(2-acrylamido-2-methyl-1-
depending on the initial precursors formulation and the propanesulfonic acid) (PAMPS). These hydrogels exhibit a liquid-
processing route followed28. Although highly conducting and to-solid transition, which can be effectively used to x
transparent materials based on graphene have already the orientation and spatial distribution of the m-rGO akes
been obtained using processing pathways such as transfer after the magnetically driven assembly process (see Fig. 1d,

2 NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078 ARTICLE

a Exfoliated magnetic
Graphite Fe3O4 reduced graphene oxide
Exfoliated graphene oxide (m-rGO)
OH
O OH
O HO OH
HO OH
O
BSA
HO
HO

O O

Hummers HO
O Hydrazine 80C, 20 h
HO HO
method O OH
OH

b c

d
Control over the Control over the
orientation spatial distribution

Horizontal
H

Static Localization
magnet on the template
z

x
y

Vertical

55 C 55 C Co or Ni
template

Drying Control of the Dispersion Control of spatial Drying

Viscosity

Viscosity
orientation of m-rGO distribution
Solid
Solid Gelling Liquid Gelling Solid
d
25 25 55 55 55 25 25
Temperature (C)

Figure 1 | Preparation of graphene-based composite lms with predened architectures. (a) Synthesis of hydrophilic magnetically responsive reduced
graphene oxide (m-rGO) mediated by bovine serum albumin (BSA). Transmission electron microscopic (TEM) images of (b) exfoliated graphene oxide and
(c) m-rGO akes ((b,c) Scale bar, 1 mm) with 10-nm diameter iron oxide nanoparticles (Scale bar, 200 nm (inset)). (d) Processing of gelatin-based
composites with magnetic control over the orientation or spatial distribution of the m-rGO akes. The magnetic assembly is performed in the liquid phase
and is followed by consolidation of the matrix to yield composite materials with tailored structures at both nano- and microscales.

Supplementary Figs 2 and 3 and Supplementary Methods for orient the m-rGO akes vertically by applying low static magnetic
details of the process and applicability of the strategy to elds of 50 mT parallel to the z axis (Fig. 1d, left).
polyurethanes). Besides orientation, the spatial distribution of m-rGO akes
The obtained m-rGO akes can be deliberately aligned using can be controlled using magnetic elds exhibiting gradients in
low-cost rare-earth magnets. Biaxial horizontal alignment of the magnitude. Indeed, local gradients in magnetic eld generate
m-rGO akes in the xy-plane is achieved by applying a magnetophoretic forces that can efciently attract suspended
horizontally rotating magnetic eld36. Literature reports that particles exhibiting magnetic susceptibility different from that of
vertical orientation of anisotropic particles is nontrivial and is the surrounding liquid43. Graded magnetic elds can be easily
usually achieved by laborious and high power energy means or designed using small permanent magnets, magnetically patterned
other costly post processing techniques3942. Here we deliberately stripes or virtual magnetic moulds comprising a metallic

NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications 3

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078

template, typically nickel or cobalt, placed above a larger the gelatin matrix into a striated pattern using the low coercivity
permanent magnet (Fig. 1d right)43,44. All these methods enable magnetic stripe of a standard train ticket. After consolidating the
scalable localization of m-rGO akes in predetermined matrix, the resulting 30.7-mm-thick lm exhibits features of similar
congurations and in time scales that cannot be achieved with dimensions as the magnetic stripe, with a periodicity of 175 mm
3D printing or other lithographic methods9,45. between m-rGO-free and m-rGO-concentrated areas. To showcase
the potential of using virtual magnetic moulds to obtain m-rGO-
based composites exhibiting more complex microstructural
Orientation and spatial distribution control. We demonstrate
designs, we fabricated a template using a 250-mm-thick nickel
the ability to control the orientation and spatial distribution of
wire bended and curved into a ower-like shape. Placing the
m-rGO akes by Wide- and Small-Angle X-rays Scattering
metallic template 1 mm above a permanent magnet of 250 mT, a
measurements and optical microscopy (Fig. 2; Supplementary
virtual magnetic mould is generated, featuring magnetic eld
Fig. 4). The signicant increase in the scattering intensity from
microgradients to guide the assembly of the m-rGO akes in the
composite lms containing m-rGO akes aligned parallel to the
shape of the template. The mirrored picture of the template
X-ray beam (along the z axis) compared with a horizontal
and the optical microscopy image of the resulting 0.02 vol%
conguration is the rst evidence of the successful alignment of
m-rGO-PAMPS composite lm conrm that shape and dimension
the akes in the intended direction (Fig. 2a). In addition, in
of the virtual magnetic mould template are precisely translated to
the vertical alignment, several intense Bragg reections
the m-rGO-based composite (Fig. 2c).
emerge, characteristic of either gelatin, rGO or SPIONs
(see Supplementary Discussion), which cannot be resolved in the
horizontal alignment. Tuning transparency. Positioning m-rGO akes into
In the two examples in Fig. 2b,c we used magnetic elds to drive two-dimensional (2D) patterns through magnetic manipulation
the spatial distribution of graphene akes within the xy-plane of of diluted dispersions enables the creation of hierarchical
the composite. In Fig. 2b, the m-rGO akes are assembled within double-percolating networks (Fig. 3). At the nanoscale the

a z
p-I p-II p-III p-IV p-V Incident beam
40 Vertical alignment

200
y (pixel)

30 100
0
200 600 1,000 1,400
x (pixel)
I (q)

20 y
x
Horizontal alignment
10
200
y (pixel)

100
0 0
0.5 1 1.5 2 2.5 3 3.5 200 600 1,000 1,400
q (A1) x (pixel)

0 1 2 3 4 5

b c
Graphene composite

200
Template

175 m
Grey scale

100

0 0.6 1.2 1.8

Distance (mm)

Figure 2 | Hierarchically structured composites exhibiting controlled orientation and spatial distribution of m-rGO akes. (a) Wide-angle X-ray
Scattering (WAXS) of 0.96 vol% m-rGOgelatin composites exhibiting horizontal (black) and vertical (grey) orientation of graphene akes. Scattering
peaks correspond to the gelatin matrix (p-I in brown), the SPIONs (p-II and p-V, blue) and the graphene (p-III and p-IV, red). (b,c) Spatial control of m-rGO
akes (b) within a gelatin matrix (7.84 vol% m-rGO) using a patterned magnetic stripe (Scale bar, 2 mm) and (c) within a PAMPS matrix (0.037 vol%
m-rGO) using a virtual magnetic mould with a complex shape (Scale bar, 2 mm).

4 NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078 ARTICLE

a Width 7 m b
100
50%

80

Transparency (%)
60
Width 7 m Optically
30%
transparent Pr
40 ed
ict
io
n
Template area (%)

20

Width 50 m
28% 0
0 20 40 60 80 100
Template area (%)

c
Without
With graphene composite
composite
Width 25 m
9.5%

0 20 40 60 80 100
Template area (%)

Figure 3 | Optical transparency of hierarchical graphene-based composites assembled on mesh-like magnetic virtual moulds. (a) Optical micrographs
of PAMPS composites containing 0.065 vol% m-rGO akes assembled into mesh-like patterns of decreasing template area and different line width (Scale
bar, 100 mm). (b) The transparency of the 30-mm-thick composite lm containing 0.065 vol% m-rGO-PAMPS increases with decreasing coverage area of
the templates. (c) Demonstration of the improved optical transparency by controlling the spatial distribution of m-rGO akes within 0.75 vol% rGOgelatin
composite lms using metallic templates of different coverage areas (Scale bar, 1 mm).

network consists of an assembly of interconnected m-rGO akes, of the lm but also creates electrically conductive paths that
whereas the 2D pattern gives rise to the second network at the increase the global conductivity of the composite material (Fig. 4).
microscale. Differently from the great majority of the approaches To study this unusual combination of properties in details, we
proposed in literature, such a directed hierarchical architecture is rst investigate the local electrical conductivity of individual
an efcient strategy to control the optical transparency of stripes made by magnetically driven localization of the m-rGO
the composite lm without altering its initial composition akes (one hierarchical level, Fig. 4a). Gelatin-based composites
(see Supplementary Methods for more details about the denition with different global concentrations of graphene akes
of transparency adopted here). Similarly, colour neutrality can be concentrated in individual stripes were fabricated using a
preserved up to relatively high concentrations of graphene. To 100-mm-thick and 1-mm-wide cobalt ribbon as a virtual magnetic
illustrate this approach, we designed a series of experiments mould positioned 1 mm above a 250 mT permanent magnet. The
where 0.065 vol% m-rGO akes in PAMPS are localized into global volume fraction of rGO, fi is calculated from the density of
continuous mesh patterns of decreasing coverage area using the m-rGO akes and the coverage of iron oxide nanoparticles
10-mm-thick nickel transmission electron microscopic grids, and BSA (details in Supplementary Fig. 6 and Supplementary
directly affecting the overall transparency of the composite lm Methods). The local electrical conductivity is measured by
(Fig. 3a; Supplementary Fig. 5). The optical transparency of each contacting two electrodes on the stripe or in the matrix area (see
composite shows a good agreement with the values expected for Supplementary Fig. 7 and Supplementary Methods). For global
lms with akes covering precisely the templated area, conrm- concentrations of 0.45 vol% or lower, the local volume fraction of
ing that the absolute template area controls the transparency of graphene is not sufciently high to form a percolating network
the composite, regardless of the line thickness of the template and the composite remains insulating. Increasing the global
(Fig. 3b). The striking increase in optical transparency enabled by concentration of m-rGO akes to 0.75 vol% results in composites
our approach is further evidenced by comparing composite lms with conducting lines and insulating surrounding matrix.
containing homogeneously distributed akes with those fabri- Thus, the minimum volume fraction needed to obtain a local
cated using magnetic virtual moulds. For the same lm thickness percolating network lies between 0.45 and 0.75 vol%. To the best
of 472 mm, 0.75 vol% rGOgelatin composites with randomly of our knowledge, this is also the rst example of magnetized rGO
distributed m-rGO akes are dark and opaque, whereas lms composite exhibiting electrically conducting properties4648.
obtained by using a 28% area coverage template are 80% more The combination of individual conductive paths at the
transparent, allowing the observation of objects throughout the nanoscale into percolating patterns at a coarser length scale is
composite lm (Fig. 3c). ideal for the electrical conductivity of the resulting hierarchical
composite lms. Similar to 3D percolating networks formed in
polymer melts33, localizing the conductive elements into
Combining transparency with electrical conductivity. Locally continuous mesh-like patterns of different sizes leads to
concentrating the conductive rGO nanosheets into continuous geometrically dened 2D hierarchical networks with lowered
mesh patterns not only enhances the overall optical transparency global percolating thresholds (two hierarchical levels, Fig. 4b).

NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications 5

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078

a b Template area:
Stripe 10 % 28 % 100 %

Matrix

)
%
)

)
%

8%

00
0
0 0.5 1 1.5 2

(1

(1
c (2
i (%)

c




102

Global conductivity  (S.cm1)

102
Local conductivity  (S.cm1)

103
103
104
Stripe 1
104 Insulating
105

c (vol%)
5
10 0.5 40 %
Insulating 106
106
Matrix 107 0
107 0 50 100
108 Template area (%)
108
0 0.5 1 1.5 2 0 0.5 1 1.5 2
Global volume fraction of rGO i (%) Global volume fraction of rGO i (%)

c Template area 100% d Template area 10%

2.97 vol%
i (%) =
3.922 vol% i (%) = 0.89 vol%
5.348 vol%
3103
Global conductivity (S.cm1)
Global conductivity (S.cm1)

8105
3
210
6105

4105
1103
2105

0 0
0 0.4 0.8 1.2 0 0.4 0.8 1.2 1.6
Compressive strain (%) Compressive strain (%)

e Homogeneous rGO distribution Programmed rGO spatial distribution

Optically Electrically
+
transparent conductive

Template 10%

100
102
Global conductivity  (S.cm1)

80
103
Transparency (%)

4
10 Optically Optically 60
Electrically Electrically
5 transparent conducting transparent conducting
10
40
106
20
107
108
0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
Global volume fraction of rGO (%) Global volume fraction of rGO (%)

Figure 4 | Electric response and transparency of gelatin composite lms with magnetically driven percolation threshold. (a) Optical micrographs (Scale
bar, 500 mm) and electrical conductivity measurements demonstrating the local control over electrical conductivity by assembling a volume fraction fi (vol%)
of m-rGO akes into a stripe in gelatin composite lms (one hierarchical level). (b) Reduction of the percolation threshold fc as a function of the moulds
template area in gelatin composite lms (two hierarchical levels). Experimental global conductivity points are tted with equation (1). (c,d) Evolution of the
global conductivity under compressive strain for composite lms prepared with a magnetic template area of 100% and 10%, respectively. The dotted lines are
guides to the eyes underlining the trend. The inset in d shows a schematic drawing of the set-up, indicating the direction of the pattern and measuring
electrodes relative to the applied force. (e) Controlling the rGO spatial distribution using a magnetic template of 10% area leads to transparent and electrically
conductive gelatin lms (dark blue region, right) of otherwise opaque and insulating homogeneous lms for rGO global volume fractions of 0.650.85 vol%
(region framed in grey, left). The optical micrographs were obtained from gelatin lms containing 0.75 vol% rGO (Scale bar, 500 mm).

6 NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078 ARTICLE

Global electrical conductivities of the hierarchical networks are carbon black lled rubber54 or 0.5% in graphene and silver
measured by depositing a goldpalladium electrode spanning nanoparticles sandwich structures55, they do not possess the
the longest dimension of the templates on the surface of the optical transparency required for optoelectronic devices. The high
composite lms directly facing the magnet. To rationalize the sensitivity provided by our patterned composites indicates that
effect of the spatial distribution of m-rGO akes on the electrical the hierarchical network of m-rGO akes not only decreases the
properties of the lms, we applied the following percolation global percolation threshold but also makes the conduction paths
model49: more strongly inuenced by applied deformations. Furthermore,
the formation of a hierarchical network of modied graphene
s C  fi  fc t ; for fi 4fc ; 1
akes is also benecial to keep the high deformability of the host
where s is the global electrical conductivity, fi the global volume matrix, which otherwise becomes brittle when the akes are
fraction of rGO in the composite lm, fc the percolating homogeneously distributed. These results underline the benets
threshold, t the conductivity exponent describing the percolation that our strategy provides in adapting the mesh pattern geometry
behaviour above threshold and C an empirical constant. This and the matrix composition for advances in the eld of strain
equation is valid for the overall single percolation as well as for sensors, where high sensitivity is required in combination with
multiple percolated systems, as demonstrated both theoretically the specic requirements and design found in health-monitoring
and experimentally32,33. Fitting equation (1) to the experimental systems and integrated electronic circuits.
conductivity values conrms the expected percolating behaviour Our ability to tune and control the spatial distribution of
of the system above the threshold. Exponents t of 1.76 and 1.95 conductive paths as a means to combine optical transparency and
were obtained for composite lms fabricated from templates with electrical conductivity in the same composite is best illustrated
coverage areas of 10% and 28%, respectively. Such values are when the obtained data are displayed simultaneously in a single
lower than the expected exponent of t2D network 2  t1D plot of the relevant properties as a function of the global volume
network 2.7, where t1D network is the exponent in the case of a fraction of rGO (Fig. 4e). In composites containing
single network, equal to 1.35 in this system32,33 (Supplementary homogenously distributed graphene akes the global volume
Table 1). This probably results from the combined detrimental fractions required to achieve optical transparency and electrical
inuence of the vertical orientation of the rGO nanosheets in conductivity are mutually excluded. Instead, using an initial
composite lms with higher volume fractions of particles with the template area of 10%, rGOgelatin composite lms containing
non-conductive BSA/SPIONs coating of the nanosheets, reducing 0.65 to 0.85 vol% of rGO can be made both transparent and
the number of contact points (see Supplementary Note 1 for conductive (Fig. 4e).
details). Well-established approaches to remove surface-adsorbed
species after assembly could be used to improve further the Discussion
conductivity while maintaining the hierarchical magnetic We have demonstrated that geometrically controlling the spatial
assembly. Despite the lower exponent t, a remarkable decrease distribution and orientation of magnetically functionalized
of 40% of the percolation threshold is observed for composite graphene in polymer matrices is a simple and potentially
lms containing m-rGO akes spatially distributed over a up-scalable route for the design and fabrication of cost-effective,
template area of 10% (see Supplementary Fig. 8, Supplementary transparent and electrically conducting graphene-based
Table 2 and Supplementary Discussion for details on conductivity functional composites. The design possibilities offered by the
measurements on the opposite face of the lms). This clearly magnetic manipulation of graphene are mirrored by the great
demonstrates the potential of this method to tailor the exibility on the format of virtual magnetic moulds, allowing the
percolation threshold of conducting anisotropic particles and to creation of complex shapes with high efciency and minimal
enhance the electrical conductivity of ller-loaded polymer lms. efforts. Our results are complementary to existing approaches to
A possible further advantage of the proposed strategy is that of design conductive and transparent materials, and prove the
allowing the production of conductive and stretchable functional principle that conductive lms can made transparent
composites serving as strain sensors of high precision. Indeed, through magnetic assembly even if highly light absorbing
thanks to the intrinsic exibility of polymers, we conducted constituents such graphene are used as the conductive phase.
in-plane conned compression experiments on polydimethylsi- The implementation of such approach to the wide range of
loxane substrates covered by the gelatin m-rGO lm while polymer lms coated with metal nanowires and nanocarbon
recording the change in electrical conductivity (details in materials would enable a further increase in the electrical
Supplementary Methods and Fig. 4c,d). As the compression conductivity through the use of higher ller concentrations
strain increases, the graphene akes are brought into closer without compromising the lms optical transparency.
contact, facilitating the electron transport and thus increasing the Alternatively, the formation of a double percolation network of
local conductivity. Remarkably, the benets of the magnetically wires or nanotubes would enable the reduction of the ller
tuned percolation threshold become apparent by comparing the content without sacricing the electrical conductivity of the lm.
onset of the strain detection: a comparable detection limit of 1.1% This provides an exciting opportunity for the fabrication of
strain is reached using just 0.89 vol% m-rGO akes in lms next-generation stretchable optoelectronic sensors and devices
exhibiting 10% template area (Fig. 4d), as opposed to the that combine optimized design and materials meant to closely
2.97 vol% needed in the case of a template area of 100% (Fig. 4c). match target functions. Given the exibility of the substrate, the
In addition, above this detection limit, an increase of strain as known stretchability of graphenepolymer composites and the
small as 0.005% can be detected in 10% template area, in contrast biocompatibility of graphene56,57, potential applications that
with a minimum detectable strain of 0.16% for homogeneously could benet from such systems range broadly from bio-
distributed lms (for fi 5.35 vol%). Such a small resolution has integrated high-sensitivity strain sensors to high efciency
not yet been reported in stretchable and transparent strain conformable solar cells.
sensors used for health-monitoring devices where high strains,
typically up to 300%, is the main property targeted5052. In these
systems, an error in strain of 2% is usually limiting the Methods
Preparation of magnetic-reduced graphene oxide. Graphene oxide was
sensitivity53. Although other stretchable composites have been prepared following a documented protocol58 (see details in the Supplementary
developed that reaches a detection limit down to 0.1% strain in Methods).

NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications 7

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078

Spherical magnetite nanoparticles were synthesized by co-precipitation of 12. Li, J. & Kim, J. K. Percolation threshold of conducting polymer composites
FeSO4 and FeCl3 in the presence of NaOH. In a typical procedure, 0.25 mmol
containing 3D randomly distributed graphite nanoplatelets. Compos. Sci.
FeSO4  7H2O and 0.5 mmol FeCl3  6H2O (both from Sigma-Aldrich) were
Technol. 67, 21142120 (2007).
dissolved in 25 ml water and vigorously stirred. After heating to 60 C, 10 ml NaOH
13. Kyrylyuk, A. V. & van der Schoot, P. Continuum percolation of carbon
solution at 2 wt% was added with 250 mg of hexadecylpyridinium bromide (Fluka).
A measure of 18 ml of the GO stock solution was mixed with 2 ml of 0.5 wt% of nanotubes in polymeric and colloidal media. Proc. Natl Acad. Sci. USA 105,
the BSA protein (Sigma-Aldrich). In a following step, this suspension was stirred 82218226 (2008).
with 250 ml of 4.4 wt% SPIONs suspension for 1 h to allow for the physical 14. Moriarty, G. P., Whittemore, J. H., Sun, K. A., Rawlins, J. W. & Grunlan, J. C.
adsorption of the SPIONs at the surface of the graphene oxide sheets through Inuence of polymer particle size on the percolation threshold of electrically
interactions with the BSA. Volume of 100 ml of reducing agent hydrazine conductive latex-based composites. J. Polym. Sci. Part B Polym. Phys. 49,
monohydrate (Sigma-Aldrich) was added at 80 C for 20 h under continuous 15471554 (2011).
stirring. After cooling to room temperature, the mixtures were kept at 4 C. 15. Li, D. & Kaner, R. B. Graphene-based materials. Science 320, 11701171 (2008).
16. Toivonen, M. S., Kaskela, A., Rojas, O. J., Kauppinen, E. I. & Ikkala, O.
Ambient-dried cellulose nanobril aerogel membranes with high tensile
Fabrication of m-rGOgelatin composites. A preheated (55 C, 30 min) aqueous strength and their use for aerosol collection and templates for transparent,
solution of 20 wt% gelatin (from bovine skin, Sigma-Aldrich) was mixed with the exible devices. Adv. Funct. Mater. 25, 66186626 (2015).
corresponding volume of the suspension of m-rGO in water and stirred at 55 C. 17. Sundramoorthy, A. K., Wang, Y.-C. & Gunasekaran, S. Low-temperature
For the experiments with controlled orientation, the mixture was cast into small solution process for preparing exible transparent carbon nanotube lm for use
polyethylene moulds. A static vertical magnetic eld of 50 mT was used for the in exible supercapacitors. Nano Res. 8, 34303445 (2015).
uniaxial alignment of the graphene akes along the z axis, whereas the samples 18. Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties
with biaxially aligned akes were obtained by rotating the magnetic eld on the xy and intrinsic strength of monolayer graphene. Science 321, 385388 (2008).
plane. The samples were afterwards cooled down to room temperature and dried 19. Nair, R. R. et al. Fine structure constant denes visual transparency of
for 24 h in ambient conditions to consolidate the gelatin and x the designed
graphene. Science 320, 13081312 (2008).
architecture (Supplementary Fig. 2). Samples with controlled spatial distribution of
20. Mayorov, A. S. et al. Micrometer-scale ballistic transport in encapsulated
m-rGO akes were fabricated by casting onto a commercial magnetic stripe (train
graphene at room temperature. Nano Lett. 11, 23962399 (2011).
ticket) followed by cooling down and drying at ambient conditions (Fig. 2c). To
demonstrate the decrease of the percolation threshold with the localization of the 21. Balandin, A. A. Thermal properties of graphene and nanostructured carbon
rGO, 250 ml of m-rGOgelatin mixtures were cast into a well with bare surface, or materials. Nat. Mater. 10, 569581 (2011).
with a nickel or cobalt template covered by a Teon foil at the bottom 22. Stankovich, S. et al. Synthesis of graphene-based nanosheets via chemical
(Supplementary Fig. 5). The wells were positioned on a permanent neodymium reduction of exfoliated graphite oxide. Carbon 45, 15581565 (2007).
magnet of 250 mT (Supermagnete, Switzerland), before casting. The samples were 23. Park, S. & Ruoff, R. S. Chemical methods for the production of graphenes. Nat.
then cooled to room temperature and dried in air, overnight. Nanotechnol. 4, 217224 (2009).
24. Paton, K. R. et al. Scalable production of large quantities of defect-free few-layer
graphene by shear exfoliation in liquids. Nat. Mater. 13, 624630 (2014).
Fabrication of m-rGO-PAMPS composites. PAMPS hydrogel was synthesized 25. Yi, M. & Shen, Z. A review on mechanical exfoliation for scalable production of
according to a modied process59 (see Supplementary Methods for more details). The graphene. J. Mater. Chem. A 3, 1170011715 (2015).
monomer solution was mixed with the relevant amount of solution of m-rGO and 26. Schniepp, H. C. et al. Functionalized single graphene sheets derived from
deposited in similar wells as described previously. The nickel template conformed in splitting graphite oxide. J. Phys. Chem. B 110, 85358539 (2006).
the shape of a ower was made by twisting a nickel wire. The trio magnet, well and 27. Hu, H. et al. Preparation and electrical conductivity of graphene/ultrahigh
suspension were placed in a dark chamber and irradiated by ultraviolet light molecular weight polyethylene composites with a segregated structure. Carbon
(OmniCure Series 1000, Lumen Dynamics) for 2 min at 60% of the maximum power. 50, 45964599 (2012).
The gelled composite lms were then dried overnight at ambient temperature. 28. Zheng, Q., Li, Z., Yang, J. & Kim, J.-K. Graphene oxide-based transparent
conductive lms. Prog. Mater. Sci. 64, 200247 (2014).
Characterization methods. Characterization of the m-rGO and the composites 29. Wang, S. J., Geng, Y., Zheng, Q. & Kim, J.-K. Fabrication of highly conducting
lm is detailed in the Supplementary Methods. and transparent graphene lms. Carbon 48, 18151823 (2010).
30. Kim, K. S. et al. Large-scale pattern growth of graphene lms for stretchable
transparent electrodes. Nature 457, 706710 (2009).
Data availability. The data that support the ndings of this study are available 31. Bae, S. et al. Roll-to-roll production of 30-inch graphene lms for transparent
from the corresponding authors on request. electrodes. Nat. Nanotechnol. 5, 574578 (2010).
32. Levon, K., Margolina, A. & Patashinsky, A. Z. Multiple percolation in
conducting polymer blends. Macromolecules 26, 40614063 (1993).
References 33. Mezzenga, R. et al. Templating organic semi- conductors via self-assembly of
1. Rogers, J. A., Someya, T. & Huang, Y. Materials and mechanics for stretchable polymer colloids. Science 299, 18721874 (2003).
electronics. Science 327, 16031607 (2010). 34. Zhang, S., Deng, H., Zhang, Q. & Fu, Q. Formation of conductive networks
2. Xu, S. et al. Soft microuidic assemblies of sensors, circuits, and radios for the with both segregated and double-percolated characteristic in conductive
skin. Science 344, 7074 (2014). polymer composites with balanced properties. ACS Appl. Mater. Interfaces 6,
3. Sam, F. L. M., Mills, C. A., Rozanski, L. J. & Silva, S. R. P. Thin lm hexagonal 68356844 (2014).
gold grids as transparent conducting electrodes in organic light emitting diodes. 35. Liu, J., Fu, S., Yuan, B., Li, Y. & Deng, Z. Toward a universal adhesive
Laser Photon. Rev. 179, 172179 (2014). nanosheet for the assembly of multiple nanoparticles based on a protein-
4. Libanori, R. et al. Stretchable heterogeneous composites with extreme induced reduction/decoration of graphene oxide. J. Am. Chem. Soc. 132,
mechanical gradients. Nat. Commun. 3, 12651274 (2012). 72797281 (2010).
5. Mallikarjuna, K., Hwang, H.-J., Chung, W.-H. & Kim, H.-S. Photonic welding 36. Erb, R. M., Libanori, R., Rothfuchs, N. & Studart, A. R. Composites reinforced
of ultra-long copper nanowire network for exible transparent electrodes using in three dimensions by using low magnetic elds. Science 335, 199204 (2012).
white ash light sintering. RSC Adv. 6, 47704779 (2016). 37. Noh, Y. J. et al. Ultra-high dispersion of graphene in polymer composite via
6. Kim, K. et al. Stretchable and transparent electrodes based on in-plane solvent free fabrication and functionalization. Sci. Rep. 5, 91419148 (2015).
structures. Nanoscale 7, 1457714594 (2015). 38. Cassagnau, P. Linear viscoelasticity and dynamics of suspensions and
7. Koga, H. et al. Transparent, conductive, and printable composites consisting of molten polymers lled with nanoparticles of different aspect ratios. Polymer 54,
TEMPO-oxidized nanocellulose and carbon nanotube. Biomacromolecules 14, 47624775 (2013).
11601165 (2013). 39. Yoon, Y. et al. Vertical alignments of graphene sheets spatially and densely
8. Secor, E. B., Prabhumirashi, P. L., Puntambekar, K., Geier, M. L. & Hersam, M. piled for fast ion diffusion in compact supercapacitors. ACS Nano 8, 45804590
C. Inkjet printing of high conductivity, exible graphene patterns. J. Phys. (2014).
Chem. Lett. 4, 13471351 (2013). 40. Wu, C., Li, F., Zhang, Y. & Guo, T. Field emission from vertical graphene sheets
9. Garca-Tunon, E. et al. Printing in Three dimensions with graphene. Adv. formed by screen-printing technique. Vacuum 94, 4852 (2013).
Mater. 27, 16881693 (2015). 41. Yu, K. et al. Patterning vertically oriented graphene sheets for nanodevice
10. Sun, J., Gerberich, W. W. & Francis, L. F. Transparent, conductive polymer applications. J. Phys. Chem. Lett. 2, 537542 (2011).
blend coatings from latex-based dispersions. Prog. Org. Coatings 59, 115121 42. Cai, M. et al. Fast response, vertically oriented graphene nanosheet electric
(2007). double layer capacitors synthesized from C2H2. ACS Nano 8, 58735882
11. Celzard, A. & Mareche, J. F. Non-universal conductivity critical exponents in (2014).
anisotropic percolating media: A new interpretation. Phys. A Stat. Mech. Appl. 43. Demirors, A. F., Pillai, P. P., Kowalczyk, B. & Grzybowski, B. A. Colloidal
317, 305312 (2003). assembly directed by virtual magnetic moulds. Nature 503, 99103 (2013).

8 NATURE COMMUNICATIONS | 7:12078 | DOI: 10.1038/ncomms12078 | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms12078 ARTICLE

44. Libanori, R., Reusch, F. B., Erb, R. M. & Studart, A. R. Ultrahigh magnetically Acknowledgements
responsive microplatelets with tunable uorescence emission. Langmuir 29, We thank Chaoxu Li, Tobias Keplinger and Jozef Adamcik for experimental assistance
1467414680 (2013). and discussions. We acknowledge internal funding from ETH Zurich, the Swiss National
45. Zhang, Q. et al. Solution-processable graphene mesh transparent electrodes for Science Foundation (grant 200020_146509 and Ambizione grant PZ00P2_148040) the
organic solar cells. Nano Res. 6, 478484 (2013). Swiss Competence Center for Energy Research (SCCERCapacity Area A3: Mini-
46. Yang, J. H., Ramaraj, B. & Yoon, K. R. Preparation and characterization of mization of energy demand) as well as support by the Center for Optical and Electron
superparamagnetic graphene oxide nanohybrids anchored with Fe3O4 microscopy of ETH Zurich (ScopeM).
nanoparticles. J. Alloys Compd. 583, 128133 (2014).
47. Myekhlai, M. et al. Synthesis and characterization of the graphene- Fe3O4- Author contributions
hybrid composite. J. Nanosci. Nanotechnol. 15, 20472051 (2015). A.R.S. and R.M. conceived and supervised the study. Experiments were designed by all
48. Yan, H., Wang, R., Li, Y. & Long, W. Thermal conductivity of magnetically authors and conducted by H.L.F., S.B. and A.F.D., S.B. synthesized and characterized the
aligned graphenepolymer composites with Fe3O4-decorated graphene modied graphene akes and conducted the scattering experiments. H.L.F. and A.F.D.
nanosheets. J. Electron. Mater. 44, 658666 (2014). designed and performed the magnetic patterning experiments and conductivity measure-
49. Stauffer, D. Scaling theory of percolation clusters. Phys. Rep. 54, 174 (1979). ments together. H.L.F. prepared the composites and characterized their transparency and
50. Cai, L. et al. Super-stretchable , transparent carbon nanotube-based capacitive electrical conductivity. H.L.F. designed the gures; and H.L.F., R.L, A.R.S. and R.M. wrote
strain sensors for human motion detection. Sci. Rep. 3, 19 (2013). the paper. H.L.F., S.B. and A.F.D. wrote the Supplementary Information. All authors
51. Hwang, B. et al. Transparent stretchable self-powered patchable sensor analysed the data and discussed their implications and critically revised the manuscript at
platform with ultrasensitive recognition of human activities. ACS Nano 9, all stages.
88018810 (2015).
52. Liu, H. et al. Electrically conductive thermoplastic elastomer nanocomposites at
ultralow graphene loading levels for strain sensor applications. J. Mater. Chem. Additional information
C 4, 157166 (2015). Supplementary Information accompanies this paper at http://www.nature.com/
53. Li, C. et al. Flexible CNT-array double helices strain sensor with high naturecommunications
stretchability for motion capture. Sci. Rep. 5, 18 (2015).
Competing nancial interests: The authors declare no competing nancial interests.
54. Wu, X., Han, Y., Zhang, X. & Lu, C. Highly sensitive , stretchable , and
wash-durable strain sensor based on ultrathin conductive layer @ Reprints and permission information is available online at http://npg.nature.com/
polyurethane yarn for tiny motion monitoring. Appl. Mater. Interfaces 8, reprintsandpermissions/
99369945 (2016).
55. Chen, S., Wei, Y., Yuan, X., Lin, Y. & Liu, L. A highly stretchable strain sensor How to cite this article: Le Ferrand, H. et al. Magnetic assembly of transparent and
based on a graphene/silver nanoparticle synergic conductive network and a conducting graphene-based functional composites. Nat. Commun. 7:12078
doi: 10.1038/ncomms12078 (2016).
sandwich structure. J. Mater. Chem. C 4, 43044311 (2016).
56. Chae, S. H. & Lee, Y. H. Carbon nanotubes and graphene towards soft
electronics. Nano Converg. 1, 1541 (2014). This work is licensed under a Creative Commons Attribution 4.0
57. Servant, A. et al. Graphene-based electroresponsive scaffolds as polymeric International License. The images or other third party material in this
implants for on-demand drug delivery. Adv. Healthc. Mater. 3, 13341343 article are included in the articles Creative Commons license, unless indicated otherwise
(2014). in the credit line; if the material is not included under the Creative Commons license,
58. Li, C., Adamcik, J. & Mezzenga, R. Biodegradable nanocomposites of amyloid users will need to obtain permission from the license holder to reproduce the material.
brils and graphene with shape-memory and enzyme-sensing properties. Nat. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
Nanotechnol. 7, 421427 (2012).
59. Gong, J. P. Why are double network hydrogels so tough? Soft Matter 6,
25832590 (2010). r The Author(s) 2016

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