Sinha 2017
Sinha 2017
Sinha 2017
*
S Supporting Information
Figure 1. (a) Structure of PEDOT:PSS; (b) Additives of screen-printing formulation: (1) Dimethyl sulfoxide (DMSO) and (2) Triton X-100; (c)
Screen-printing schematic; (d) The dimensions of the ECG electrodes; (e) PEDOT:PSS electrodes printed on a t-shirt; (f) Image of testing the t-
shirt while exercising; and (g) ECG waveforms obtained from PEDOT:PSS electrodes on t-shirt (blue line) and Ag/AgCl electrodes (red dashed
line) under different heart rates: (1) 80 bpm, (2) 110 bpm, (3) 140 bpm, (4) 150 bpm, (5) 180 bpm, and (6) 120 bpm.
delustering agent, when fully soaked with PEDOT:PSS has hydrogel consisting of an electrolyte, and an adhesive that helps
been shown to have high current carrying capacities of ca. 10 in establishing skin contact. PEDOT:PSS is known to be a
A/mm2.18 Considering that every three units in PEDOT carry a mixed conductor25 in which PEDOT is responsible for
positive charge, which is stabilized by one unit of negative electronic conductivity, and PSS contributes to ionic
charge on PSS, calculations suggest that approximately 4 out of conductivity, both of which are necessary for transduction of
every 5 units of styrene sulfonic acid in polystyrenesulfonate are the ECG signal. Screen-printed PEDOT:PSS electrodes on a t-
unbound (S2, Supporting Information). These unbound groups shirt present an interesting material for monitoring the
are available to react with the fabric through a covalent bond cardiovascular activity of an athlete, not only during sedentary
between the silanol groups contained in the silica and the free conditions but also during exercise.
sulfonic acid groups of polystyrene sulfonic acid (PSSH). The A viscous formulation of commercially available PEDOT:PSS
pKa value of sulfonic acid groups in PSS has been reported to (PH 1000), DMSO, and Triton X-100 was used for screen
be 1 and that of silanols in silica to be 6.8.19,20 Pokrovsky and printing (Figure 1(c)). The solid content was obtained from
co-workers21 studied the protonation of silanol groups and thermogravimetric analysis (TGA) (Figure S1, Supporting
suggested the existence of Si(OH2)+ at an extremely low pH Information). The design of the electrodes on the t-shirt is
(0−3). Wet PEDOT:PSS on fabric will cause protonation of shown in Figure 1(d). One subject was recruited to test the
silanol groups, which, followed by condensation with sulfonic viability of the electrode for measuring the ECG signal during
acid, leads to the formation of sulfo-silyl esters leading to the exercise on a treadmill. An elastic chest strap was used to
covalent bond formation with the fabric. Otley and co-workers enhance skin contact with the electrodes. Ag/AgCl electrodes
proposed this reaction and its role in the phase separation of were used as a control to simultaneously measure ECG along
PEDOT:PSS, resulting in low sheet resistances of silica- with printed PEDOT:PSS electrodes. Figure 1(g) shows the
containing fabrics coated with PEDOT:PSS.18 The reaction ECG signal obtained from a subject under various exercising
of free sulfonic acid groups of PSS has later been suggested by conditions. A discernible ECG signal was obtained with printed
Cho and co-workers.22 This nanoparticle-induced phase electrodes under dry skin conditions during the start of the
separation leading to low sheet resistances can be used to exercise. The amplitude of this signal increased with an increase
make organic wires and biopotential electrodes, having current in the level of physical activity. When the subject was in
carrying capacities approaching copper. Other techniques that recovery, the amplitude of the ECG signal remained the same
involve functionalization of textiles include grafting23 and cross- (Figure 1(g)-6). The increase in the amplitude of the signal
linking24 for self-cleaning, antimicrobial, and water capture could be attributed to transpiration of water vapor from the
properties. skin during exercise leading to decrease in skin contact
In this paper, we describe the development of a conductive t- impedance. This observation is further substantiated by the
shirt for monitoring ECG signals using commercially available results obtained from the electrochemical impedance spectros-
materials and screen-printing technique without the use of a copy, which shows that the electrode impedance of
hydrogel or an adhesive around the electrodes. Typically, PEDOT:PSS fabric drops when the fabric is fully soaked in
commercial ECG electrodes consist of a Ag/AgCl electrode, a water (Figure S2, Supporting Information). This reduced
37525 DOI: 10.1021/acsami.7b09954
ACS Appl. Mater. Interfaces 2017, 9, 37524−37528
ACS Applied Materials & Interfaces Letter
Figure 2. (a) Variation of sheet resistance and amount of PEDOT:PSS with an increasing number of screen-printed layers. (b) Overlay of ECG
signals obtained from two different electrode-wire configurations with Ag/AgCl electrodes: PEDOT:PSS wire (blue line) and copper wire (orange
line). (c) (1) Reaction scheme of the silanol group with the sulfonic acid of PSS to form silyl sulfonate ester and (2) SEM image of PEDOT:PSS-
coated fabric electrode. (d) Variation in skin contact impedance of different electrodes: PEDOT:PSS electrode in dry conditions (red line),
commercially available Ag/AgCl electrode (blue line), and PEDOT:PSS fabric electrode with lotion on skin (black). (e) ECG responses of different
electrodes under different skin conditions from subject 1: PEDOT:PSS electrode in dry skin conditions (red line), PEDOT:PSS electrode with
lotion on skin (black line), and Ag/AgCl (blue dash-dot line) at rest. (f) ECG response from a screen-printed PEDOT:PSS electrode with
PEDOT:PSS wire with lotion on skin at rest.
contact impedance existed even after completion of exercise protons can be lost from PEDOT:PSS coated on fabrics to
because of the hydrophilicity of PSS in PEDOT:PSS. The water and/or sweat in contact with the fabric; however, the
cross-correlation indices of ECG templates between the conditions tested here do not model conditions of a fabric in
fabricated sensors and Ag/AgCl electrodes were approximately contact with skin. A more detailed study would be required to
83%, even in S4 and S5, where there are high motion artifacts. assess the toxicity of PEDOT−PSS.
The average heart rate was calculated by measuring the R−R To understand the material aspects of the wearable ECG
interval and was found to be as high as 180 bpm (Figure S3, sensor, a systematic study was carried out to replace
Supporting Information) which corresponds to heart rate components of a typical ECG setup, which currently includes
during high intensity interval training (HIIT). HIIT is generally copper wires and Ag/AgCl electrodes. An optimization study
done at a heart rate that is 85%−95% of the maximum heart was done by screen printing PEDOT:PSS on nonwoven
rate (HRmax) which is calculated as HRmax = 207 − (0.7 × polyethylene terephthalate (PET) fabrics. PEDOT:PSS-coated
age),26,27 and therefore the application of this type of shirt can textile was first demonstrated to function as a wire of 1 mm
be extended to almost any age group above 15 years. To thickness with Ag/AgCl as an ECG electrode. To evaluate the
demonstrate the reusability of the t-shirt, the ECG signal was
change in resistance versus the amount of PEDOT:PSS on the
recorded at a heart rate of 170 bpm after washing the t-shirt
fabric, a maximum of five layers of 2.5 cm length and 1 mm
with commercially available detergent in a regular washing
machine followed by hot air drying (Figure S4−S5, Supporting width were printed onto PET nonwoven textile. Figure 2(a)
Information). Thus, PEDOT:PSS-based fabric electrodes are shows the change in sheet resistance of the fabric as a function
good candidates for measuring an ECG, and the applications of wire thickness. Five layers of PEDOT:PSS over an area of 25
could extend to gaming and military as well as sports medicine. mm2 having a combined mass of ca. 45 mg gave a sheet
To evaluate the skin compatibility of PEDOT:PSS, a resistance of 5.6 Ω/sq. To demonstrate the practical usage of
preliminary study was carried out to check changes in pH of the printed wires, a wire of length 10 cm and width 1 mm was
deionized water and artificial sweat solution when fabric printed onto PET. Three coatings of PEDOT:PSS were
swatches coated with PEDOT:PSS were immersed into applied, and the overall resistance of the printed wires was
solution. The pH of both the solutions changed to 3.17 from measured to be ca. 3 kΩ. This wire was then connected to a
an initial value of 6.8 for water and 3.81 from 4.27 for artificial Ag/AgCl electrode attached to the chest, and an ECG signal
sweat at 25 °C (Figure S6, Supporting Information). The only was recorded as shown in Figure 2(b). The change to
conclusion that can be drawn from these initial studies is that PEDOT:PSS wires resulted in ca. 2% loss of amplitude of the
37526 DOI: 10.1021/acsami.7b09954
ACS Appl. Mater. Interfaces 2017, 9, 37524−37528
ACS Applied Materials & Interfaces Letter
ECG signal when compared to Ag/AgCl electrodes with copper temperature from 0 to 100 °C.17 The electrodes used in this
wires of diameter 1 mm. study have a sheet resistance of ca. 5 Ω/sq and, therefore, can
Screen-printed PEDOT:PSS fabrics were then evaluated as be used to measure ECG signal in real time conditions where
electrodes for ECG application. The ECG signals collected the temperature could vary between 0 and 50 °C. Thus, screen-
from a screen-printed PEDOT:PSS fabric that has an average printing techniques combined with surface chemistry of fabrics
resistance of ca. 5 Ω/sq were then compared with that of the can be exploited to coat PEDOT:PSS with low sheet
commercially available Ag/AgCl electrode. To reduce the skin- resistances. Also, the method of screen printing is already
electrode impedance, approximately 0.5 g of Cetaphil lotion established in the industry for making organic electronic
was applied onto the skin as opposed to coating the electrode devices, which would allow for scalability in the production of
with a conducting gel. The skin contact impedances of ECG electrodes.
electrodes at 10 Hz and the frequency that corresponds to PEDOT:PSS has not yet been used before as both wires and
the QRS complex were measured to be 0.35 ± 0.04 MΩ and ECG electrodes. PEDOT:PSS electrodes were connected with
0.27 ± 0.6 MΩ for Ag/AgCl and screen-printed PEDOT:PSS PEDOT:PSS wires via snap buttons for recording ECG signals.
electrodes with lotion, respectively. This decrease in contact Drawing on conclusions from the initial ECG testing, the skin
impedance substantially affected the amplitude of the ECG was prepared by applying 0.5 g of lotion over an area on skin
signal with screen-printed electrodes, showing a 55.4% increase with length 40 cm and width 6 cm. The ECG waveform
in amplitude compared to Ag/AgCl. Figure 2(d) shows the obtained is shown in Figure 2(f). The amplitude of the signal
variation of skin contact impedance with frequency. Screen- obtained was found to be comparable with that of Ag/AgCl.
printed PEDOT:PSS electrodes with underlying lotion on the This result paves the way for organic materials to be integrated
skin have similar contact impedances to Ag/AgCl over a into wearables with the possible replacement of metals as both
frequency range of 4−150 Hz. Thus, lowering the skin contact wires and electrodes.
impedance plays a vital role in ECG recording, though a This work describes the fabrication of an all organic ECG
discernible ECG signal was still recorded with fabric electrode using a commercially available conducting polymer
PEDOT:PSS electrodes in dry skin conditions. onto commercially sold fabrics. Exploiting the mixed nature of
The contact impedance at 10 Hz was marginally lower for conduction, PEDOT:PSS-based electrodes were shown to
PEDOT:PSS electrodes with lotion on the skin than with dry record ECG signal in dry condition. The formation of sulfo-
electrodes, which further translates to variations in amplitude of silyl esters has been attributed to low sheet resistances of ca. 5
ECG signal, as shown in Figure 2(e). Takamatsu and co- ohm/sq leading to low thermal noise. Screen-printed
workers coated an ionic liquid gel on PEDOT:PSS electrodes PEDOT:PSS electrodes on a t-shirt were shown to record
on a knitted fabric and found that the impedance was 2.5 times ECG signal under physical activity at a heart rate of 180 bpm.
lower than that of Ag/AgCl electrodes.12 Pani and co-workers28 Increased ionic conductivity brought about by transpiration of
matched the ECG signal obtained from a dip-coated water results in an increase in the amplitude of the signal.
PEDOT:PSS polyester electrode to Ag/AgCl by using a PEDOT:PSS demonstrated the ease of processing in that it can
commercially available ECG gel on the skin and by wetting be used as an organic wire as well as an electrode, resulting in a
the electrode with saline. These results indicate that signal comparable to Ag/AgCl electrode. By integrating these
PEDOT:PSS acts as a transducer, even in dry conditions, and electrodes, wires, and potentially more complex circuitry
its performance can be improved by preparing the skin with directly into fabrics, smart clothing could be developed for
lotion or by sweating. continuous monitoring in both athletes and patients having
cardiovascular risk, increasing their quality of life.
■
The complications in ECG signals are caused by unwanted
motion artifacts and noise. While the motion artifacts of a Ag/
AgCl electrode have been alleviated by adhesive around the ASSOCIATED CONTENT
electrode, the motion artifacts of PEDOT:PSS-based fabric *
S Supporting Information
electrodes have not been fully explored. In this study, the The Supporting Information is available free of charge on the
conformity of the compression t-shirt onto the skin ensured ACS Publications website at DOI: 10.1021/acsami.7b09954.
that electrodes stayed in place during measurements which Experimental details and procedures, fabrication of ECG
were further reinforced by a chest strap. The other factor which electrodes, and measurement of ECG signal (PDF)
■
affects the quality of the ECG signal is the thermal noise, which
is generated by the inherent resistive characteristic of AUTHOR INFORMATION
PEDOT:PSS and is proportional to square root of its resistance
Corresponding Author
for a given bandwidth.29 The signal-to-noise ratio (SNR) of the
*E-mail: g.sotzing@uconn.edu.
PEDOT:PSS fabrics with a sheet resistance of 5 ohm/sq was
found to be ca. 15.42 dB under dry skin conditions which ORCID
increased to ca. 29.59 dB upon application of lotion on skin. Sneh K. Sinha: 0000-0003-0555-0282
Takamatsu and co-workers12 reported the value as ca. 16.3 dB Notes
for their electrodes coated with a cross-linked gel and having a The authors declare no competing financial interest.
sheet resistance of 220 ohm/sq. Bihar and co-workers30 found
the SNR to be ca. 11.01 dB for three layers of inkjet-printed
PEDOT:PSS on paper. This result points out how the
■ ACKNOWLEDGMENTS
This work was supported in part by the Office of Naval
resistance, in the form of thermal noise, together with skin Research work unit N00014-15-1-2236.
contact impedance influences the signal quality. The signal
becomes noisy with an increase in resistance of the electrode
(Figure S7, Supporting Information). Additionally, the
■ REFERENCES
(1) World Health Organization Global Status Report on Non-
resistance of PEDOT:PSS-coated fabric is not affected by communicable Diseases. 2014.
(2) McAdams, E. T.; Jossinet, J.; Lackermeier, A.; Risacher, F. Factors (19) Lewis, S. R.; Datta, S.; Gui, M.; Coker, E. L.; Huggins, F. E.;
Affecting Electrode-Gel-Skin Interface Impedance in Electrical Daunert, S.; Bachas, L.; Bhattacharyya, D. Reactive Nanostructured
Impedance Tomography. Med. Biol. Eng. Comput. 1996, 34 (6), Membranes for Water Purification. Proc. Natl. Acad. Sci. U. S. A. 2011,
397−408. 108 (21), 8577−8582.
(3) Gruetzmann, A.; Hansen, S.; Müller, J. Novel Dry Electrodes for (20) Schindler, P.; Kamber, H. R. Die Acidität von Silanolgruppen.
ECG Monitoring. Physiol. Meas. 2007, 28 (11), 1375−1390. Vorläufige Mitteillung. Helv. Chim. Acta 1968, 51 (7), 1781−1786.
(4) Myers, A. C.; Huang, H.; Zhu, Y. Wearable Silver Nanowire Dry (21) Pokrovsky, O. S.; Golubev, S. V.; Mielczarski, J. A. Kinetic
Electrodes for Electrophysiological Sensing. RSC Adv. 2015, 5 (15), Evidences of the Existence of Positively Charged Species at the
11627−11632. Quartz-Aqueous Solution Interface. J. Colloid Interface Sci. 2006, 296
(5) Kim, T.; Park, J.; Sohn, J.; Cho, D.; Jeon, S. Bioinspired, Highly (1), 189−194.
Stretchable, and Conductive Dry Adhesives Based on 1D−2D Hybrid (22) Cho, N.; Diekhans, J.; Steward, M.; Bakr, O. M.; Choi, S. A
Carbon Nanocomposites for All-in-One ECG Electrodes. ACS Nano Facile Micropatterning Method for a Highly Flexible PEDOT: PSS on
2016, 10 (4), 4770−4778. SU-8. Org. Electron. 2016, 34, 75−78.
(6) Yapici, M. K.; Alkhidir, T.; Samad, Y. A.; Liao, K. Graphene-Clad (23) Yang, H.; Zhu, H.; Hendrix, M. M. R. M.; Lousberg, N. J. H. G.
Textile Electrodes for Electrocardiogram Monitoring. Sens. Actuators, B M.; de With, G.; Esteves, A. C. C.; Xin, J. H. Temperature-Triggered
2015, 221, 1469−1474. Collection and Release of Water from Fogs by a Sponge-Like Cotton
(7) Noh, Y.; Bales, J. R.; Reyes, B. A.; Molignano, J.; Clement, A. L.; Fabric. Adv. Mater. 2013, 25 (8), 1150−1154.
Pins, G. D.; Florian, J. P.; Chon, K. H. Novel Conductive Carbon (24) Zhong, Q.; Chen, Y. Y.; Guan, S. L.; Fang, Q. S.; Chen, T.;
Black and Polydimethlysiloxane ECG Electrode: A Comparison with Müller-Buschbaum, P.; Wang, J. P. Smart Cleaning Cotton Fabrics
Commercial Electrodes in Fresh, Chlorinated, and Salt Water. Ann. Cross-Linked with Thermo-Responsive and Flexible poly(2-(2-
Methoxyethoxy)ethoxyethyl Methacrylate-Co-Ethylene Glycol Meth-
Biomed. Eng. 2016, 44 (8), 2464−2479.
acrylate). RSC Adv. 2015, 5 (48), 38382−38390.
(8) Reyes, B. A.; Posada-Quintero, H. F.; Bales, J. R.; Clement, A. L.;
(25) Rivnay, J.; Inal, S.; Collins, B. A.; Sessolo, M.; Stavrinidou, E.;
Pins, G. D.; Swiston, A.; Riistama, J.; Florian, J. P.; Shykoff, B.; Qin,
Strakosas, X.; Tassone, C.; Delongchamp, D. M.; Malliaras, G. G.
M.; Chon, K. H. Novel Electrodes for Underwater ECG Monitoring.
Structural Control of Mixed Ionic and Electronic Transport in
IEEE Trans. Biomed. Eng. 2014, 61 (6), 1863−1876. Conducting Polymers. Nat. Commun. 2016, 7, 11287.
(9) Taji, B.; Shirmohammadi, S.; Groza, V.; Batkin, I. Impact of Skin- (26) Karlsen, T.; Aamot, I.-L.; Haykowsky, M.; Rognmo, Ø. High
Electrode Interface on Electrocardiogram Measurements Using Intensity Interval Training for Maximizing Health Outcomes. Prog.
Conductive Textile Electrodes. IEEE Trans. Instrum. Meas. 2014, 63 Cardiovasc. Dis. 2017, 60 (1), 67−77.
(6), 1412−1422. (27) Tanaka, H.; Monahan, K. D.; Seals, D. R. Age-Predicted
(10) Wang, J.; Chen, Y.; An, J.; Xu, K.; Chen, T.; Müller-Buschbaum, Maximal Heart Rate Revisited. J. Am. Coll. Cardiol. 2001, 37 (1), 153−
P.; Zhong, Q. Intelligent Textiles with Comfort Regulation and 156.
Inhibition of Bacterial Adhesion Realized by Cross-Linking Poly(N (28) Pani, D.; Dessi, A.; Saenz-Cogollo, J. F.; Barabino, G.; Fraboni,
-Isopropylacrylamide- Co -Ethylene Glycol Methacrylate) to Cotton B.; Bonfiglio, A. Fully Textile, PEDOT: PSS Based Electrodes for
Fabrics. ACS Appl. Mater. Interfaces 2017, 9 (15), 13647−13656. Wearable ECG Monitoring Systems. IEEE Trans. Biomed. Eng. 2016,
(11) Guo, Y.; Otley, M. T.; Li, M.; Zhang, X.; Sinha, S. K.; Treich, G. 63 (3), 540−549.
M.; Sotzing, G. A. PEDOT: PSS “Wires” Printed on Textile for (29) Fitch, P. Signal/Noise Ratio in the Recording of Human Nerve-
Wearable Electronics. ACS Appl. Mater. Interfaces 2016, 8 (40), Action Potentials. Med. Biol. Eng. 1973, 11 (2), 146−154.
26998−27005. (30) Bihar, E.; Roberts, T.; Saadaoui, M.; Hervé, T.; De Graaf, J. B.;
(12) Takamatsu, S.; Lonjaret, T.; Crisp, D.; Badier, J.-M.; Malliaras, Malliaras, G. G. Inkjet-Printed PEDOT: PSS Electrodes on Paper for
G. G.; Ismailova, E. Direct Patterning of Organic Conductors on Electrocardiography. Adv. Healthcare Mater. 2017, 6, 1601167.
Knitted Textiles for Long-Term Electrocardiography. Sci. Rep. 2015, 5,
15003.
(13) Papaiordanidou, M.; Takamatsu, S.; Rezaei-Mazinani, S.;
Lonjaret, T.; Martin, A.; Ismailova, E. Cutaneous Recording and
Stimulation of Muscles Using Organic Electronic Textiles. Adv.
Healthcare Mater. 2016, 5 (16), 2001−2006.
(14) Rivnay, J.; Leleux, P.; Ferro, M.; Sessolo, M.; Williamson, A.;
Koutsouras, D. A.; Khodagholy, D.; Ramuz, M.; Strakosas, X.; Owens,
R. M.; Benar, C.; Badier, J.-M.; Bernard, C.; Malliaras, G. G. High-
Performance Transistors for Bioelectronics through Tuning of
Channel Thickness. Sci. Adv. 2015, 1 (4), e1400251.
(15) Palumbiny, C. M.; Heller, C.; Schaffer, C. J.; Körstgens, V.;
Santoro, G.; Roth, S. V.; Mü l ler-Buschbaum, P. Molecular
Reorientation and Structural Changes in Cosolvent-Treated Highly
Conductive PEDOT: PSS Electrodes for Flexible Indium Tin Oxide-
Free Organic Electronics. J. Phys. Chem. C 2014, 118 (25), 13598−
13606.
(16) Oh, J. Y.; Shin, M.; Lee, J. B.; Ahn, J.-H.; Baik, H. K.; Jeong, U.
Effect of PEDOT Nanofibril Networks on the Conductivity,
Flexibility, and Coatability of PEDOT: PSS Films. ACS Appl. Mater.
Interfaces 2014, 6 (9), 6954−6961.
(17) Sotzing, G. A. Electrically Conductive Synthetic Fiber and Fibrous
Substrate, Method of Making, and Use Thereof; U.S. Patent 9644313 B2,
2017.
(18) Otley, M. T.; Alamer, F. A.; Guo, Y.; Santana, J.; Eren, E.; Li,
M.; Lombardi, J.; Sotzing, G. A. Phase Segregation of PEDOT: PSS on
Textile to Produce Materials of > 10 A mm −2 Current Carrying
Capacity. Macromol. Mater. Eng. 2017, 302, 1600348.