View Article Online

View Journal

Journal of
Materials Chemistry C
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: A. Zucca, K.
Yamagishi, T. Fujie, S. Takeoka, V. Mattoli and F. Greco, J. Mater. Chem. C, 2015, DOI:
10.1039/C5TC00750J.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.

Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/materialsC
 View Article Online
Page 1 of 11 Journal of Materials Chemistry C DOI: 10.1039/C5TC00750J

Journal Name RSC

ARTICLE

Journal of Materials Chemistry C Accepted Manuscript

Roll to Roll Processing of Ultraconformable
Conducting Polymer Nanosheets
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

A. Zucca,†a,b K. Yamagishi,†c T. Fujie,* c,d S. Takeoka,c,d V. Mattoli* a and F.

Greco* a

Thin and compliant conductive materials and electronic devices that are able to stand as
free-standing membranes or to conform to surfaces are relevant for the development of
human-device interfaces and unperceivable skin-contact personal health monitoring systems.
In this work, a roll-to-roll (R2R) process for the preparation of conductive polymer
nanosheets on large areas has been developed in view to move such technology towards
real-world applications. R2R conductive nanosheets are obtained as free -standing structures
through release from a temporary substrate and then transferred in conformal contact to any
target surface with arbitrary shape, curvature and surface topography (including biological
tissue such as skin). A specific high-conductivity formulation of PEDOT:PSS has been
optimized for skin-contact applications, by making use of butylene glycol (BG) as dopant: a
dermatologically approved ingredient. The R2R nanosheets were tested as unperceivable
surface electromyography electrodes able to record muscle electric activity. The present
R2R process has advantageous properties such as continuous, high throughput printing on
large area rolls, cost-effectiveness, speed of execution and use of industry-ready/mass-scale
manufacturing technology.

Introduction combination of functional (mainly electronic) and structural

properties. Technology related to organic and printed
Smart electronic skin 1, novel sensing2, actuation and energy electronics is growing at a fast pace not only towards
harvesting systems3-5 finding application in consumer production of organic photovoltaics, flexible displays, OLED
electronics, energy, robotics and biomedicine 6-8 have been lighting –which constitute the major part of efforts for
made possible thanks to the improvements in the so-called field translating technology from lab-scale development to early
of “flexible, stretchable and conformable electronics”. Such production- but also towards more innovative applications, as
smart electronics includes thin and compliant conductive in the case of stretchable/conformable electronics, organic
materials and electronic devices that are able to sustain bioelectronics and biointegrated technologies.6, 12, 18-24
bending/twisting/stretching or also to adhere and conform to Applications in cited fields, indeed, could take full advantage of
surfaces.1, 9 At the same time, industrialization of these the peculiar features offered by organic and printed electronics,
technologies combining to the conventional film fabrication by combining a new class of functional materials and large-
technique (e.g., R2R) is of crucial importance towards real- area, high-volume deposition and patterning techniques.
world applications of the smart electronics. In this framework, our group focused on the development of
Technological progresses are particularly relevant for the ultra-thin, ultra-conformable and conductive polymeric films
development of human-device interfaces, implanted bio- (referred to as “conductive nanosheets”) based on poly(3,4-
electronics or unperceivable skin-contact personal health ethylenedioxythiophene) : poly(styrenesulfonate)
monitoring systems10-13. In this regard, a variety of conformable (PEDOT:PSS).25 Free-standing polymer nanosheets have
electronic devices that can be transferred on the skin unique physical properties such as ultra-conformability and
(“epidermal electronics”14 for thermal monitoring of the human physical adhesiveness to biological tissues (e.g., skin, organs)
skin15 or epidermal hydration sensing 16, 17) have been recently due to their ultra-thin and flexible structure (tens- to hundreds-
proposed, based on microfabrication of traditional inorganic of-nanometre thickness with several square centimetres area),
materials embedded within thin elastomeric substrates. as in the case of PLLA nanosheets.26-28 We previously found
In alternative approaches, organic conductors and that the conductive nanosheets also possessed the similar
semiconductors are considered because of the suitable structural and physical properties, that can be released in water

This journal is © The Royal Society of Chemistry 2015 J. Name., 2015, 00, 1-3 | 1
 View Article Online
Journal of Materials Chemistry C Page 2 of 11
DOI: 10.1039/C5TC00750J
ARTICLE Journal Name

from their temporary substrate, manipulated as free-standing to print the ink on the desired flexible substrate. The gravure
films, and recollected onto virtually any surface. 25 Moreover, roll is partially immersed in the ink container and during the
various lab-scale deposition and patterning techniques rotation it draws ink out of the ink container with it. A blade
permitted to embed circuits on board of nanosheets 29 and to pushes and scrapes the roll before to contact the substrate in
demonstrate their utility as ultrathin actuators and sensors. 30, 31 order to remove the excess of polymer. Then the substrate

Journal of Materials Chemistry C Accepted Manuscript

Recently, we extended such technology to a temporary transfer moves between the impression roll and the gravure roll; the
conductive tattoo which was successfully employed as an impression roll applies a force and pushes the substrate on the
unperceivable dry electrode for surface electromyography gravure roll allowing the transfer of the ink. Then, a hot air
(sEMG).32 flow drier included along the R2R line, provides a thermal
In view to further expand application of conductive nanosheets treatment on the ink for drying it, thus obtaining a dry,
and to move such technology towards real-world scenarios, in homogeneous polymer film. The flexible substrate coated with
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

this study, we focus on a roll-to-roll (R2R) process technique film is finally collected in an output roll, by recovering it on a
for the preparation of conductive polymer nanosheets with large reel.
area (several thousands of square centimetre). The present R2R The 1L samples were fabricated by two steps of R2R process
process (gravure coating based) has advantageous properties deposition and adopting a sacrificial layer technique in order to
such as continuous, high throughput printing on large rolls, release the free-standing PEDOT:PSS film in acetone. During
large area patterning/processing, cost-effectiveness, speed of the first step a sacrificial layer of cellulose acetate has been
execution and use of industry-ready/mass-scale manufacturing deposited on a poly(ethylene terephthalate) (PET) film
technology. We choose the R2R gravure approach because of substrate; then, the layer of PEDOT: PSS was deposited on top
the relative simplicity and because of the availability of a small of the sacrificial layer. The addition of 1% of fluorosurfactant
scale facility in our labs, nevertheless it should be possible to Zonyl® to the pristine PEDOT:PSS water-based solution was
extend the methodology to other R2R techniques. The R2R necessary in order to improve its wetting and homogeneous
conductive nanosheets can be released from a temporary spreading on the substrate. Due to the limited size of our lab-
substrate and obtained as free-standing, i.e. they are stable and scale R2R equipment, the in-line thermal treatment provided
able to support themselves without the need for any support. from the drier resulted too fast and not sufficient for both
Then, they can be transferred in conformal contact to any target drying and annealing of PEDOT:PSS. For this reason samples
surface with arbitrary shape, curvature and surface topography underwent a further off-line annealing in oven at 140 °C for 15
(e.g. skin). The release and transfer is provided through dry minutes in order to make PEDOT:PSS insoluble in water and
peeling or wetting with water, depending on the specific increase its conductivity. It is important to note that, by
formulation, with the overall transfer process being similar to operating the same procedure with a suitable R2R equipment –
that of temporary transfer tattoos. In addition, we also made use i.e. one having a properly designed length of line exposed to
of BG, a dermatologically approved ingredient, as a secondary hot air flow (drier)- the complete thermal treatment can be
dopant of the conductive nanosheet for skin-contact application. operated in line in a single step with a time estimated around
The present R2R nanosheets have several advantageous 60 - 180 s depending on air flow temperature, thus excluding
characteristics, such as strength, flexibility, ability to adhere to the need for an off-line post thermal treatment. 1L nanosheets
different substrates; moreover, given the selected formulation, were released from the PET substrate thanks to the dissolution
they could promise high biocompatibility, which could make in acetone of the sacrificial layer of cellulose acetate.
them suitable for numerous different technological applications. On the other hand, the 2L nanosheets were fabricated on top of
In particular they could be applied in the biomedical field, as in polypropylene (PP) flexible films by two steps of R2R process
the development of sensors and other skin-contact electronic deposition: a first layer of PDLLA on PP substrate and a second
devices and in large area flexible electronics manufacturing. layer of PEDOT:PSS on top of the first layer (Fig. 1c, steps i –
iii, and Fig. 1 d). In this case, a PP substrate was preferred to a
Results and discussion PET substrate because the adhesive interaction between
PDLLA and PP are weaker with respect to those between
R2R process and transfer of free-standing nanosheets PDLLA and PET and this allowed to detach the nanosheet from
By using a lab-scale R2R equipment (Gravure roll coating, Fig. PP by peeling with the aid of an adhesive tape frame. This dry
1a, b) we optimized the process to fabricate: 1) single layer detachment method (Fig. 1c, steps iv – v) is particularly
PEDOT:PSS nanosheets (1L) and 2) bilayer interesting as it does not involve the use of any solvent and
PEDOT:PSS/PDLLA nanosheets (2L). For both types of permits easy manipulation of free-standing films until their
nanosheets we prepared and compared results obtained with transfer on target surfaces. The adhesive tape was placed on top
pristine PEDOT:PSS formulation (no dopants), DMSO doped of the 2L nanosheet still supported on PP; then, with the aid of
and BG doped formulations. tweezers, the bilayer was detached from the substrate obtaining
In summary, the R2R process (scheme in Fig. 1a) is a freestanding membrane supported by an adhesive tape frame
characterized by the deposition of a polymer solution (ink) by (steps iv-v, Fig. 1c and Fig. 1e). The nanosheet was then
using a roll (gravure roll) with an engraved texture that allows temporarily transferred onto a piece of nylon mesh (step vi) that
allows the subsequent detachment and transfer of the nanosheet

2 | J. Name., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
 View Article Online
Page 3 of 11 Journal of Materials Chemistry C DOI: 10.1039/C5TC00750J
Journal Name ARTICLE

on the skin by wetting its surface with water, in a similar Due to their ultra-low thickness and composition, nanosheets
fashion of a temporary transfer tattoo (steps vii-ix, Fig. 1c). In are characterized by stable and conformal adhesion to a variety
the case of 1L nanosheets, they can be recollected on the same of different surfaces -such as tissues or soft and rigid materials
mesh from release baths where they float free-standing (Fig. 1 with complex topography and non-planar shapes- while
e) and then transferred according to the same vi-ix steps. A maintaining their conductive functionality. These features are

Journal of Materials Chemistry C Accepted Manuscript

video showing the sequence of peeling, transfer and release on very important for the envisioned applications in the field of
skin is available as Supporting Information (SI1). skin-contact electronics. Some examples of very large area
nanosheets transferred on human skin are provided in Fig. 1f.
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

Fig. 1 Schematic view of R2R gravure roll coating technique (a) and picture of the lab-scale R2R equipment. Scheme of processing, release and transfer steps for 1L
and 2L conductive nanosheets (c). d) Pictures of PP rolls on which 2L conductive nanosheets have been fabricated. e) Free-standing nanosheet peeled off from
temporary substrate by means of an adhesive tape frame. f) Example of conductive nanosheet transferred on skin.

Thickness of nanosheets could be controlled by setting R2R

Structural and electrical characterization process parameters. In the case of 1L nanosheets thickness was

This journal is © The Royal Society of Chemistry 2015 J. Name., 2015, 00, 1-3 | 3
 View Article Online
Journal of Materials Chemistry C Page 4 of 11
DOI: 10.1039/C5TC00750J
ARTICLE Journal Name

varied in the range 60 - 150 nm by changing the gravure roll Conductivity σ of nanosheets was investigated by using a 4-
rotation speed used in the R2R deposition (Fig. 2a). Similar point probe measurement system on square samples. Addition
results were obtained for all of three PEDOT:PSS compositions to PEDOT:PSS of secondary dopants such as ethylene glycol,
taken in consideration –i.e. pristine (no dopants), DMSO doped dimethyl sulfoxide, sorbitol or others in a typical range of 1−10
and BG doped- with a linearly increasing thickness with wt. % content is known to greatly enhance the electronic

Journal of Materials Chemistry C Accepted Manuscript

increasing gravure roll speed. As regards 2L nanosheets, conductivity of dried films. 33-35 To this aim, we added a 5 wt. %
PEDOT:PSS layer deposition was set to 25 rpm gravure roll of DMSO or BG to the original PEDOT:PSS formulation. BG
speed, and overall thickness was varied by varying the PDLLA was especially selected for skin-contact applications of
concentration in the solution used for gravure roll coating (Fig. conductive nanosheets since it is normally used as an additive
2b). The thickness of single layer PDLLA nanosheet is reported in several cosmetic products to be applied on skin, and thus
for a purpose of useful comparison. Overall thickness of 2L promises possible biocompatibility.36 A comparison of the
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

nanosheets was in the range 180 - 380 nm, which included a conductivity σ of the 1L nanosheets made with pristine
PDLLA layer with thickness in the range of 70-170 nm. PEDOT:PSS and doped PEDOT:PSS is reported in Fig. 2c.
Thickness of PDLLA layer was found to linearly increase as
PDLLA concentration was increased from 1 - 2 wt.%.

Fig. 2 a) Thickness of 1L nanosheets as a function of gravure roll speed in R2R process; b) thickness of 2L nanosheets as a function of PDLLA concentration in R2R
process; c) conductivity of nanosheets as a function of thickness; comparison among different formulations of the conductive layer: PEDOT:PSS (open squares),
PEDOT:PSS+BG (grey circles), PEDOT:PSS+DMSO (black circles). Evaluation of adhesive strength of nanosheets on Si surface with a scratch tester: Normalized Critical

4 | J. Name., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
 View Article Online
Page 5 of 11 Journal of Materials Chemistry C DOI: 10.1039/C5TC00750J
Journal Name ARTICLE

Load for d) 1L nanosheets, comparison among PDLLA (various thickness depending on PDLLA concentration) and PEDOT:PSS; 2L nanosheets with BG e) and DMSO f)
as doping agents in PEDOT:PSS, comparison among nanosheets at different thickness for PDLLA and PEDOT:PSS side.

The doping effect of both DMSO and BG is clearly difference in the adhesion properties would be attributed to the
demonstrated with typical conductivity enhanced by three order mechanical properties of each nanosheet surface. Considering

Journal of Materials Chemistry C Accepted Manuscript

of magnitude with respect to pristine PEDOT:PSS. This that adhesive strength of nanosheets increases as elastic
conductivity enhancement is totally in line with expectations modulus decreases, 27 PEDOT:PSS nanosheets (< 1 GPa) may
and values reported in literature for PEDOT:PSS films show higher adhesive strength than the PDLLA nanosheets (~3
containing similar dopants and deposited on bulk substrates.34, GPa)25, 42.
37
Conductivity of the ultra-thin PEDOT:PSS nanosheets
slightly increased by increasing thickness, as already observed Stability of nanosheets on skin: mechanical stress and sweat
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

for nanosheets with similar thickness range. This evidence was Because one of the envisioned applications of R2R conductive
rationalized by considering the onset of some percolation effect nanosheets is as skin-contact unperceivable electrodes, we
arising at low thickness, comparable with typical dimension of studied how their electric properties are affected when collected
primary PEDOT-rich particles.25, 38 on human skin. A first source of variation and/or damage to the
integrity of nanosheets and to their functional behaviour could
Adhesive strength come from mechanical stress, in particular during exercising.
Further characterization of R2R nanosheets involved the Particularly severe conditions apply when the target area for
assessment of their adhesive properties. Indeed, once placement of the nanosheet electrode is on rather
nanosheets are recollected on target surfaces –onto which they stretchable/movable parts of the body; in such cases a wearable
conform because of ultra-low-thickness- they are characterized device can be subjected to relatively high levels of
by stable adhesion and interfacing, mainly due to Van Der stretching/bending/compression. To this purpose, we assessed
Waals interaction between surface and nanosheets. The the stability and evolution of electrical resistance of nanosheets
adhesion properties of the nanosheets has been evaluated by placed on the wrist and on the finger, contacted with Au coated
investigating the relationship between the critical load polyimide thin sheet electrode and subjected to repetitive cycles
necessary for their detachment from the substrate and their of flexion/exercise. These target body parts are indeed selected
thickness, by using a scratch tester for thin films. 39 as most representative of severe mechanical constraints. Results
A diamond tip gradually scratched the nanosheet collected onto of the experiments are summarized in Fig. 3a. It is interesting to
a Si wafer causing the detachment from the substrate thereafter notice that when subjected to repeated stimulation up to 250
measured from obtained images. We evaluated the adhesion cycles, only negligible irreversible variations of electrical
properties both of 1L and 2L nanosheets. In the latter case, each resistance were observed in the case of wrist
side of the PEDOT:PSS/PDLLA bilayer nanosheet (with (expansion/contraction on a +42/-42° range with respect to
pristine PEDOT:PSS formulation) was tested. relaxed state – 0°) and minor variations (up to 20%) in the case
As a general trend, the adhesion strength increased as thickness of finger contraction, where nanosheet was placed across distal
decreased both for 1L and for 2L nanosheets (Fig. 2d, e, f). This phalanges (flexion 70°). Such a variation of electrical resistance
trend is consistent with the adhesive properties of other single can be ascribed to the formation of cracks that partially
layer nanosheets such as poly(L- lactic acid) (PLLA) and interrupt the structural integrity of the nanosheet.
poly(lactic-co-glycolic acid) (PLGA).40, 41 For free-standing Moreover, by visually inspecting the nanosheet surface and the
nanosheets with thickness less than 100 nm, we observed nanosheet/electrode interface after cyclic exercising we were
higher potential to adhere to several substrates without any kind able to recognize that cracks are mostly formed at the
of reagents or surface functionalization. This adhesion property nanosheet/electrode interface: indeed interfacing of the ultrathin
strongly decreased as thickness increased. Indeed as concerns nanosheet with a considerably thicker (13 μm) and stiffer
PDLLA nanosheets (Fig. 2d), the critical load varied from ~ Au/polyimide electrode can cause ruptures along the edge.
40000 N/m for a thickness of ~ 70 nm to ~ 22000 N/m for a Furthermore, visual inspection of nanosheet worn on the skin of
thickness around 170 nm. Instead, the 1L PEDOT:PSS subjects for a longer period and during exercising (a football
nanosheet (thickness ~ 110 nm) showed higher critical load match) did not evidenced the formation of cracks (Fig. 3b).
compared with PDLLA nanosheets (Fig. 2d). Thus it is expected that even better performances in term of
Regarding the 2L nanosheets, by comparing the results resistance stability to mechanical stress can be obtained if
obtained between the opposite sides of the nanosheets, a higher suitable solutions for contacting are addressed. A second source
critical load was found for the PEDOT:PSS side rather than the of variation/degradation of electrical performances for
PDLLA side, for both BG (Fig. 2e) and DMSO (Fig. 2f) doped electrodes worn on skin could come from sweating. In order to
PEDOT:PSS, respectively. The difference in normalized critical assess the nanosheet stability against sweating nanosheets were
load between PEDOT:PSS surface and PDLLA surface slightly immersed in a bath containing water or artificial sweat at two
increased by increasing the thickness of PDLLA layer, while no different pH levels (namely pH 5.5 – often referred to as
significant variations of adhesion trends were observed for “physiological skin pH”- and pH 8, representative of basic
different formulations of PEDOT:PSS. It is suggested that conditions encountered, for example, during aging or in

This journal is © The Royal Society of Chemistry 2015 J. Name., 2015, 00, 1-3 | 5
 View Article Online
Journal of Materials Chemistry C Page 6 of 11
DOI: 10.1039/C5TC00750J
ARTICLE Journal Name

presence of some pathologies 43), and their electrical resistance carrier density and the carrier mobility due to alkaline
was monitored over time up to 3 h of immersion. While components (such as NaOH).45 Nevertheless, despite the harsh
structural integrity was preserved (Fig. 3 c i), an increase in condition of experiments, which are worse than real sweating
electrical resistance was observed in all cases (Fig. 3c, iii), with condition on skin, the nanosheets demonstrated to fully retain
lower variation recorded for immersion in water (R/R 0 ~ 2 after their structural integrity and at least partially retain their

Journal of Materials Chemistry C Accepted Manuscript

3 h). Physiological condition (pH 5.5) caused a variation of functional properties. In order to compare the stability against
R/R0 ~ 3 after 3 h, while basic conditions (pH 8) were more sweating of nanosheets with that of other skin-contact
aggressive, with a distinct variation R/R 0 ~ 7-8 after 3 h. electrodes, a standard pregelled sEMG electrode was immersed
Reduced stability of the conductive properties of PEDOT:PSS in a bath containing artificial sweat at pH 8.0 for 3 h. The
in a basic environment have been reported previously, and pregelled electrode was irreversibly damaged as clearly
ascribed to oxidative processes 44 or to the decrease of the evidenced in pictures (Figure 3 c ii).
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

Fig. 3 Evaluation of function/stability on skin of BG doped 2L nanosheets. a) Stability against mechanical stress: electrical resistance variation R/R 0 during repeated
exercise for finger contraction (nanosheet placed on distal phalanges, flexion 70° respect to relaxed state) and wrist contra ction/expansion (nanosheet placed on
wrist, flexion +42/-42° respectively respect to relaxed state). b) Evaluation of nanosheet integrity for a nanosheet worn on the skin of a subject during exercise
(football match). c) Stability against sweating: pictures of samples before (left) and after (right) immersion for 3 h in artificial sweat (pH 8.0) in the case of 2L
nanosheet (i) and standard pregelled sEMG electrode (ii); (iii) evolution during time of electrical resistance variation R/R 0 of nanosheets collected on a silicone replica
of skin and submerged in a bath containing water (squares), artificial sweat - pH 5.5 (squares) and pH 8.0 (triangles).

6 | J. Name., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
 View Article Online
Page 7 of 11 Journal of Materials Chemistry C DOI: 10.1039/C5TC00750J
Journal Name ARTICLE

A method was presented for the fabrication of single layer (1L)

Operation of nanosheets as sEMG electrodes and bilayer (2L) conductive nanosheets with a R2R process,
As a preliminary demonstration of applications of the present characterized by high throughput and capability to operate on
nanosheets as on-skin electrodes for personal healthcare very large area. Nanosheets can be obtained as free-standing
monitoring, we tested their performances as dry surface membranes after release from a temporary substrate with a wet

Journal of Materials Chemistry C Accepted Manuscript

electromyography (sEMG) electrodes. By using a standard (sacrificial layer) or dry (mechanical peeling off) methods, and
EMG setup connected to conductive nanosheets adhered on used as ultra-thin ultraconformable electrodes. Three different
skin through thin Au coated plastic foils, we were able to record formulations of the conducting polymer layer were optimized
the electric activity of muscles on the arm of one healthy and tested for achieving different grades of conductivity and to
subject. Experiments were performed in parallel also with address the requirements of specific applications. In particular
standard pregelled Ag/AgCl sEMG electrodes used in clinical an high conductivity grade formulation was demonstrated
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

practice, to provide a meaningful comparison. Stepwise making use of a dermatologically safe doping agent (BG), to be
increment of the sEMG signals were recorded as a function of used for skin-contact applications of the present nanosheets.
the pressure applied by a hand grasping an analogue pressure Nanosheets were characterized as regards their structure and
gauge (Fig. 4a), while no sEMG signals were recorded after their functional properties also on skin and a first proof of
removal of the nanosheets (Fig. 4b). Notably, comparable principle demonstration of operation as dry sEMG electrodes
results were obtained, especially in terms of signal to noise was presented.
ratio (SNR). Such promising results are totally in line with These findings could open the way to the development of free-
those recently obtained in the case of PEDOT:PSS temporary standing ultrathin conductive membranes and of unperceivable
transfer tattoos.32 The demonstrated capability of nanosheets to and low-cost on-skin electrodes for applications in sports,
act as dry sEMG electrodes could open the way toward wellness and healthcare.
healthcare monitoring application as well as to fascinating
fields of use of EMG as in the case of prosthetic limbs.46, 47 Experimental
Materials.
Rolls of poly(propylene) (PP) (TORAYFAN® 2500H) with a
thickness of 40 μm and poly(ethylene-terephtalate) (PET)
(Lumirror® T60) with a thickness of 25 μm were purchased
from Toray and were used as received as substrates for
nanosheet preparation. A PEDOT:PSS aqueous dispersion,
Clevios PH1000 (1:2.5 PEDOT:PSS ratio; H.C. Starck GmbH,
Leverkusen, Germany) has been employed after filtration
(MILLEX average pore size 0.8 µm, MILLIPORE). Poly (D,L-
lactic acid) (PDLLA, Mw = 330- 600 kDa) was purchased from
Polysciences Inc. and used as received. Cellulose acetate (CA,
average Mw = 30 kDa) was purchased from Sigma-Aldrich and
used as received. Ethyl acetate (≥99.5%, Wako Pure Chemical
Industries, Ltd), dimethyl sulfoxide (DMSO, Wako Pure
Chemical Industries, ≥99%), acetone (≥99%, Wako Pure
Chemical Industries), Zonyl® FS- 300 Fluorosurfactant
(laboratory grade, Sigma- Aldrich) were used without any other
purification.

Fabrication of Single Layer PEDOT:PSS R2R Nanosheets.

PEDOT:PSS nanosheets were prepared by using a sacrificial
layer technique, by properly modifying the process reported
elsewhere. CA (c = 20 mg/ml in acetone) was used as the
sacrificial layer and it was deposited on a PET film substrate by
a roll to roll (R2R) process technique at 30 rpm (gravure roll
Fig. 4 sEMG recording of muscle activity (contraction) on the arm of a healthy rotation) with a line speed of 1.3 m/min and then dried at 80 °C,
subject: a) comparison between 2L BG-doped nanosheets and standard with an hot air flow included in the R2R line. The PET film
pregelled electrodes, and b) comparison between no nanosheets and pregelled
electrodes. Signal to noise ratio (SNR) of a recorded signal demonstrating similar
coated with CA was obtained in a roll, after recovery by
performances. winding on a reel. The PEDOT:PSS acqueous dispersion
(Clevios PH 1000) was mixed with DMSO (5 wt. %) or with
BG (5 wt.%) and Zonyl FS- 300 (1 v/V %) for 8 h at RT with
Conclusions

This journal is © The Royal Society of Chemistry 2015 J. Name., 2015, 00, 1-3 | 7
 View Article Online
Journal of Materials Chemistry C Page 8 of 11
DOI: 10.1039/C5TC00750J
ARTICLE Journal Name

the aid of a magnetic stirrer and then deposited using a R2R nanosheet was detected (designated a critical load). The critical
process technique over the dried CA layer. The gravure roll loads were measured on nanosheets collected onto fresh silicon
rotation was varied in the range between 5 rpm and 45 rpm for wafer and the measures were performed on single layer
obtaining nanosheets with different thicknesses, while line PEDOT:PSS, PDLLA single layer nanosheets and
speed was kept constant at 0.2 m/min. Then samples underwent PDLLA/PEDOT:PSS bilayer nanosheets by changing thickness

Journal of Materials Chemistry C Accepted Manuscript

a short thermal treatment at 130 °C with an hot air flow of the PDLLA layer. Critical loads were normalized by dividing
integrated in the R2R line and re-reeled. A subsequent thermal the obtained values by the nanosheet thickness.
treatment in oven at 140 °C for 15 minutes was imposed to the
roll. PEDOT:PSS nanosheets were finally released in acetone Evaluation of stability of the nanosheets as skin-contact
after the dissolution of CA layer. electrodes.
Experiments were performed on 2L nanosheets with
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

Fabrication of Bilayer PEDOT:PSS/PDLLA R2R Nanosheets. PEDOT:PSS including BG as a dopant. Stability and evolution
PEDOT:PSS/PDLLA bilayer nanosheets were prepared by of electrical resistance of nanosheets subjected to repetitive
using a R2R process technique. PDLLA (c = 1- 1.5- 2 wt. % in cycles of flexion/exercise on skin was assessed by placing
ethyl acetate) was deposited onto a PP film substrate at 25 rpm, square samples on the wrist and on the finger of one subject.
a line speed of 1.3 m/min and then dried at 80 °C with an air Electric contact with nanosheets was provided by two Au
flow in R2R line. The PP film coated with PDLLA was coated polyimide thin sheet (thickness 13 μm) placed at
obtained in a roll, after recovery by winding on a reel. The opposite edges of nanosheet. The resistance across electrode
PEDOT: PSS acqueous dispersion (Clevios PH 1000) was and nanosheet was recorded with a digital multimeter during
mixed with DMSO (5 wt. %) or with BG (5 wt.%) and Zonyl (1 exercising (flexion) of wrist and distal phalanges of finger.
V/ v %) for 8 h at RT with the aid of a magnetic stirrer and Stability of nanosheets against sweating was assessed by
deposited using a R2R process technique over the cured prolonged (up to 3 h) immersion of nanosheet samples in water
PDLLA layer at 35 rpm (gravure roll rotation) with a line speed and artificial sweat (JIS L0848, Isekyu) at pH 5.5 and pH 8.0.
of 0.2 m/min and then dried with an air flow in R2R line at 130 The 2L nanosheets were adhered to an artificial skin model
°C. A post thermal treatment in oven at 110 °C was carried out (Product No. 47, Inner arm model from woman, Beaulax) with
on the re-reeled roll. The bilayers of PEDOT: PSS/ PDLLA PEDOT:PSS side bottom. Electrical contact between a
were peeled from the PP substrate by using tape attached on the nanosheet and a digital multimeter was provided with two
edges of the nanosheet. pieces of conductive copper tape sealed on the skin model. The
skin model with adhered nanosheet was immersed in MilliQ
Thickness, Surface and Electrical Characterization. water, acidic (pH 5.5) artificial sweat solution, or alkaline (pH
Thickness of the conductive polymer nanosheets was obtained 8.0) artificial sweat solution and the resistance across the
by Atomic Force Microscope (AFM) imaging, operating in nanosheet was recorded at the period of 1, 3, 5, 10, 15, 30, 45,
tapping mode (MFP-3D-BIO, Asylum Research Co., Santa 60, 90, 120, 150, and 180 min after immersion. Measurements
Barbara, CA). Measurements were performed in air, at room were taken on three different samples for each.
temperature, on samples collected and dried on a fresh silicon
wafer after the release of the nanosheet. The thickness t was sEMG experiments.
measured by scratching the nanosheet with a needle. From 2L nanosheets with PEDOT:PSS including BG as a dopant
AFM topographic imaging between the nanosheet and the were tested as dry sEMG electrodes. Circular samples
scratched domain (scan range area 20 x20 μm 2) it was possible (diameter 2 cm) were placed on top of the upper arm of a
to quantify the thickness of the nanosheet, by measuring the healthy subject. Standard pregelled Ag/AgCl sEMG disposable
height profile of the edge. electrodes (gel area diameter 2 cm; Eurotrode) were placed in
The electrical characterization of the nanosheets was carried out parallel to the nanosheets for comparison. The subject was
with a four-point technique on square samples with lateral asked to grasp an analog pressure gauge in hand. (North Coast
dimension of 1.5 cm. Sheet resistance Rs was measured and the Medical, Morgan Hill, CA) and to maintain the grip force at
related conductivity σ has been calculated making use of three levels (1, 3, 5 pounds/in.2, psi) as indicated by the gauge,
formulae: Rs = π/ln2 (V/i); σ = 1/ Rs t. while the EMG was being recorded. The contraction and
relaxation of the muscle were repeated alternately for three
Adhesive Properties Characterization of the Nanosheets. times for each pressure level. The sEMG signals were acquired
The adhesion strength of the conductive nanosheets was by using a versatile amplifier (EMG-USB2+, OT
measured by a scratch tester for thin films (model CSR-02, Bioelettronica) and the original data were analyzed by Excel
Rhesca, Tokyo) with the following procedure: a diamond tip 2013, Microsoft. The SNR was calculated by taking the highest
with a radius of curvature of 100 μm was continuously and EMG signal peak (As) during active period and the standard
vertically loaded at a rate of 10 mN/min, and used to deviation (STD) of the background (An) during inactive period.
horizontally scratch the conductive nanosheet readsorbed on the From these values, the SNR was calculated by the following
SiO2 substrate (scratch length: 100 μm, scratch rate: 10 mm/s). formula:
The signal of frictional vibration just after breaking of the

8 | J. Name., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
 View Article Online
Page 9 of 11 Journal of Materials Chemistry C DOI: 10.1039/C5TC00750J
Journal Name ARTICLE

s
R (d ) = 20 log10 . 11. D.-H. Kim, J. Viventi, J. J. Amsden, J. Xiao, L. Vigeland, Y.-S. Kim,
J. A. Blanco, B. Panilaitis, E. S. Frechette, D. Contreras, D. L.
Acknowledgements Kaplan, F. G. Omenetto, Y. Huang, K.-C. Hwang, M. R.
The help of Dr. Sudha (Istituto Italiano di Tecnologia) for Zakin, B. Litt and J. A. Rogers, Nature Materials, 2010, 9,
providing suitable means of contacting nanosheets on skin is 511-517.

Journal of Materials Chemistry C Accepted Manuscript

acknowledged. Dr. Christian Cipriani and Mr. Sergio Tarantino 12. D. Khodagholy, T. Doublet, M. Gurfinkel, P. Quilichini, E.
(The iorobotics Institute, Scuola Superiore Sant’Anna, Pisa, Ismailova, P. Leleux, T. Herve, S. Sanaur, C. Bernard and G.
Italy) are acknowledged for their help in sEMG experiments. G. Malliaras, Advanced Materials, 2011, 23, H268-H272.
This work was supported in part by JSPS Core-to-Core
13. P. Leleux, J.-M. Badier, J. Rivnay, C. Bénar, T. Hervé, P. Chauvel
Program (K.Y., T.F. and S.T.) from MEXT, Japan, Institute of
Advanced Active Aging Research, Waseda University (K.Y., and G. G. Malliaras, Advanced Healthcare Materials, 2013,
n/a-n/a.
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

T.F. and S.T.), the Leading Graduate Program in Science and

Engineering, Waseda University from MEXT, Japan (K. Y.), 14. D. H. Kim, N. Lu, R. Ma, Y. S. Kim, R. H. Kim, S. Wang, J. Wu, S.
and Mitsubishi Materials Research Grant (T.F.). M. Won, H. Tao, A. Islam, K. J. Yu, T. I. Kim, R. Chowdhury,
M. Ying, L. Xu, M. Li, H. J. Chung, H. Keum, M.
Notes and references McCormick, P. Liu, Y. W. Zhang, F. G. Omenetto, Y. Huang,
a
Center for Micro-BioRobotics@SSSA, Istituto Italiano di Tecnologia,
T. Coleman and J. A. Rogers, Science, 2011, 333, 838-843.
Viale R. Piaggio 34, 56025, Pontedera, Italy. Email:
[email protected], [email protected] 15. R. C. Webb, A. P. Bonifas, A. Behnaz, Y. Zhang, K. J. Yu, H.
b
The iorobotics Institute, Scuola Superiore Sant’Anna, Viale R. Piaggio Cheng, M. Shi, Z. Bian, Z. Liu, Y.-S. Kim, W.-H. Yeo, J. S.
34, 56025, Pontedera, Italy.
c Park, J. Song, Y. Li, Y. Huang, A. M. Gorbach and J. A.
Graduate School of Advanced Science and Engineering, Waseda
University, TWIns, 2-2 Wakamatsu-cho, Shinjuku, Tokyo 162-8480, Rogers, Nature Materials, 2013, 12, 938-944.
Japan. Email: [email protected]. 16. H. Cheng, Y. Zhang, X. Huang, J. A. Rogers and Y. Huang, Sensors
d
Institute of Advanced Active Aging Research, Waseda University,
and Actuators A: Physical, 2013, 203, 149-153.
TWIns, 2-2 Wakamatsu-cho, Shinjuku, Tokyo 162-8480, Japan.
17. X. Huang, Y. Liu, H. Cheng, W.-J. Shin, J. A. Fan, Z. Liu, C.-J. Lu,
† These authors equally contributed to work G.-W. Kong, K. Chen, D. Patnaik, S.-H. Lee, S. Hage-Ali, Y.
Electronic Supplementary Information (ESI) available: Huang and J. A. Rogers, Advanced Functional Materials,
Supporting Video 1 shows a demonstration of peeling off, handling and 2014, 24, 3846-3854.
release on skin of a 2L conductive nanosheet. 18. T. Sekitani, U. Zschieschang, H. Klauk and T. Someya, Nature
See DOI: 10.1039/b000000x/ Materials, 2010, 9, 1015-1022.
19. T. Sekitani, S. Iba, Y. Kato, Y. Noguchi, T. Someya and T. Sakurai,
1. S. Bauer, Nat Mater, 2013, 12, 871-872. Applied Physics Letters, 2005, 87, 1-3.
2. H. Tao, M. A. Brenckle, M. Yang, J. Zhang, M. Liu, S. M. Siebert, R. 20. M. Kaltenbrunner, T. Sekitani, J. Reeder, T. Yokota, K. Kuribara, T.
D. Averitt, M. S. Mannoor, M. C. McAlpine, J. A. Rogers, D. Tokuhara, M. Drack, R. Schwödiauer, I. Graz, S. Bauer-
L. Kaplan and F. G. Omenetto, Advanced Materials, 2012, 24, Gogonea, S. Bauer and T. Someya, Nature, 2013, 499, 458-
1067-1072. 463.
3. R. D. Kornbluh, R. Pelrine, H. Prahlad, A. Wong-Foy, B. McCoy, S. 21. M. Kaltenbrunner, M. S. White, E. D. Głowacki, T. Sekitani, T.
Kim, J. Eckerle and T. Low, MRS Bulletin, 2012, 37, 246-253. Someya, N. S. Sariciftci and S. Bauer, Nat Commun, 2012, 3,
4. W. Jia, G. Valdés-Ramírez, A. J. Bandodkar, J. R. Windmiller and J. 770.
Wang, Angewandte Chemie, 2013, 125, 7374-7377. 22. D. J. Lipomi, B. C. K. Tee, M. Vosgueritchian and Z. Bao, Advanced
5. S. Bauer, S. Bauer-Gogonea, I. Graz, M. Kaltenbrunner, C. Keplinger Materials, 2011, 23, 1771-1775.
and R. Schwödiauer, Advanced Materials, 2014, 26, 149-162. 23. M. Vosgueritchian, D. J. Lipomi and Z. Bao, Advanced Functional
6. T. Someya, Stretchable Electronics, 2012. Materials, 2012, 22, 421-428.
7. D.-H. Kim, J. Xiao, J. Song, Y. Huang and J. A. Rogers, Advanced 24. D. Khodagholy, J. N. Gelinas, T. Thesen, W. Doyle, O. Devinsky, G.
Materials, 2010, 22, 2108-2124. G. Malliaras and G. Buzsaki, Nat Neurosci, 2015, 18, 310-315.
8. T. Someya, Y. Kato, T. Sekitani, S. Iba, Y. Noguchi, Y. Murase, H. 25. F. Greco, A. Zucca, S. Taccola, A. Menciassi, T. Fujie, H. Haniuda,
Kawaguchi and T. Sakurai, Proceedings of the National S. Takeoka, P. Dario and V. Mattoli, Soft Matter, 2011, 7,
Academy of Sciences of the United States of America, 2005, 10642-10650.
102, 12321-12325. 26. T. Fujie, Y. Okamura and S. Takeoka, Advanced Materials, 2007, 19,
9. M. L. Hammock, A. Chortos, B. C. K. Tee, J. B. H. Tok and Z. Bao, 3549-3553.
Advanced Materials, 2013, 25, 5997-6038. 27. T. Fujie, N. Matsutani, M. Kinoshita, Y. Okamura, A. Saito and S.
10. J. Viventi, D.-H. Kim, L. Vigeland, E. S. Frechette, J. A. Blanco, Y.- Takeoka, Advanced Functional Materials, 2009, 19, 2560-
S. Kim, A. E. Avrin, V. R. Tiruvadi, S.-W. Hwang, A. C. 2568.
Vanleer, D. F. Wulsin, K. Davis, C. E. Gelber, L. Palmer, J. 28. T. Fujie and S. Takeoka, in Nanobiotechnology, eds. D. A. Phoenix
Van der Spiegel, J. Wu, J. Xiao, Y. Huang, D. Contreras, J. A. and A. Waqar, One Central Press, United Kingdom, 2014, pp.
Rogers and B. Litt, Nat Neurosci, 2011, 14, 1599-1605. 68-94.
29. F. Greco, A. Zucca, S. Taccola, B. Mazzolai and V. Mattoli, ACS
Applied Materials & Interfaces, 2013, 5, 9461-9469.

This journal is © The Royal Society of Chemistry 2015 J. Name., 2015, 00, 1-3 | 9
 View Article Online
Journal of Materials Chemistry C Page 10 of 11
DOI: 10.1039/C5TC00750J
ARTICLE Journal Name

30. S. Taccola, F. Greco, B. Mazzolai, V. Mattoli and E. W. H. Jager,

Journal of Micromechanics and Microengineering, 2013, 23.
31. S. Taccola, F. Greco, A. Zucca, C. Innocenti, C. De Julián Fernández,
G. Campo, C. Sangregorio, B. Mazzolai and V. Mattoli, ACS
Applied Materials and Interfaces, 2013, 5, 6324-6332.

Journal of Materials Chemistry C Accepted Manuscript

32. A. Zucca, C. Cipriani, S. Sudha, S. Tarantino, D. Ricci, V. Mattoli
and F. Greco, Advanced Healthcare Materials, 2015.
33. J. Huang, P. F. Miller, J. S. Wilson, A. J. de Mello, J. C. de Mello and
D. D. C. Bradley, Advanced Functional Materials, 2005, 15,
290-296.
34. I. Cruz-Cruz, M. Reyes-Reyes, M. A. Aguilar-Frutis, A. G.
Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

Rodriguez and R. López-Sandoval, Synthetic Metals, 2010,

160, 1501-1506.
35. A. M. Nardes, R. A. J. Janssen and M. Kemerink, Advanced
Functional Materials, 2008, 18, 865-871.
36. W. Fan, T. Kinnunen, A. Niinimäki and M. Hannuksela, American
Journal of Contact Dermatitis, 1991, 2, 181-183.
37. S. K. M. Jönsson, J. Birgerson, X. Crispin, G. Greczynski, W.
Osikowicz, A. W. Denier van der Gon, W. R. Salaneck and M.
Fahlman, Synthetic Metals, 2003, 139, 1-10.
38. D. M. DeLongchamp, B. D. Vogt, C. M. Brooks, K. Kano, J. Obrzut,
C. A. Richter, O. A. Kirillov and E. K. Lin, Langmuir, 2005,
21, 11480-11483.
39. S. Baba, T. Midorikawa and T. Nakano, Applied Surface Science,
1999, 144–145, 344-349.
40. Y. Okamura, K. Kabata, M. Kinoshita, D. Saitoh and S. Takeoka,
Advanced Materials, 2009, 21, 4388-4392.
41. X. Shi, T. Fujie, A. Saito, S. Takeoka, Y. Hou, Y. Shu, M. Chen, H.
Wu and A. Khademhosseini, Advanced Materials, 2014, 26,
3290-3296.
42. T. Fujie, Y. Kawamoto, H. Haniuda, A. Saito, K. Kabata, Y. Honda,
E. Ohmori, T. Asahi and S. Takeoka, Macromolecules, 2013,
46, 395-402.
43. F. Herrmann and L. Mandol, The Journal of Investigative
Dermatology, 1955, 24, 225-246.
44. T. A. R. Skotheim, John R, ed., Conjugated Polymers: Processing
and Applications, CRC Press, Boca Raton, 2007.
45. M. M. De Kok, M. Buechel, S. I. E. Vulto, P. Van De Weyer, E. A.
Meulenkamp, S. H. P. M. De Winter, A. J. G. Mank, H. J. M.
Vorstenbosch, C. H. L. Weijtens and V. Van Elsbergen,
Physica Status Solidi (A) Applied Research, 2004, 201, 1342-
1359.
46. C. Cipriani, C. Antfolk, M. Controzzi, G. Lundborg, B. Rosen, M. C.
Carrozza and F. Sebelius, Neural Systems and Rehabilitation
Engineering, IEEE Transactions on, 2011, 19, 260-270.
47. K. Nazarpour, C. Cipriani, D. Farina and T. Kuiken, Neural Systems
and Rehabilitation Engineering, IEEE Transactions on, 2014,
22, 711-715.

10 | J. Name., 2015, 00, 1-3 This journal is © The Royal Society of Chemistry 2015
 Page 11 of 11 Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C5TC00750J

Journal of Materials Chemistry C Accepted Manuscript

Published on 13 May 2015. Downloaded by Carleton University on 13/05/2015 16:03:11.

A roll-to-roll process is reported for the preparation of free-standing conductive polymer nanosheets on large
areas. Nanosheets are transferred in conformal contact to target surfaces (including skin) and act as
unperceivable bio-electrodes.
80x40mm (300 x 300 DPI)