Journal of

Electroanalytical Chemistry
Journal of Electroanalytical Chemistry 573 (2004) 4348 www.elsevier.com/locate/jelechem

Electrochemical polymerization and properties of PEDOT/S-EDOT on neural microelectrode arrays

Yinghong Xiao
a b

a,b

, Xinyan Cui c, David C. Martin

a,d,e,*

Department of Materials Science and Engineering, The University of Michigan, Ann Arbor, MI, USA Department of Materials Science and Engineering, Nanjing University of Science and Technology, 200, Xiaolingwei, Nanjing 210014, China c Department of Bioengineering, University of Pittsburgh, Pittsburgh, PA, USA d Department of Biomedical Engineering, The University of Michigan, Ann Arbor, MI, USA e Macromolecular Science and Engineering Center, The University of Michigan, Ann Arbor, MI, USA Received 31 March 2004; received in revised form 18 June 2004; accepted 22 June 2004 Available online 29 July 2004

Abstract The conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) doped with its derivative sulfonatoalkoxy EDOT (SEDOT) was electrochemically polymerized on the surface of electrodes along the shank of microfabricated neural probes. Reective Fourier transform infrared spectroscopy demonstrated the composition of the resultant polymer. Examinations of scanning electron microscope images of the lms indicated that the surface morphology was rough and the thickness varied with deposition time. The magnitude of the impedance of the PEDOT/S-EDOT coated electrode was lower than that of bare gold over a wide range of frequencies from 1 to 105 Hz. The roughness of the electrode surface resulted in a resistive component being added to the double layer capacitance. Cyclic voltammetry demonstrated the intrinsic redox reaction and the increased charge capacity of the PEDOT/SEDOT coated electrodes. 2004 Elsevier B.V. All rights reserved.
Keywords: Electrochemical polymerization; Conducting polymer; Surface morphology; Impedance spectroscopy

1. Introduction Neural probes are multichannel neural microelectrode arrays micromachined with special techniques [1,2]. These devices facilitate the functional stimulation of and recording from the peripheral and central nervous system. However, when implanted in brain tissue, these devices need modication on the surface of the electrodes in order to improve the signal transport at the electrodejtissue interface. Several aspects of the interface need to be optimized for better performance. The electrochemical impedance, the surface area and the biocompatibility of the electrode material all need
Corresponding author. Tel.: +1-734-936-3161; fax: +1-508-2568352. E-mail address: milty@umich.edu (D.C. Martin). 0022-0728/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jelechem.2004.06.024
*

to be considered. In this study, gold was used as the electrode site material due to its well-known biocompatibility and inertness in electrochemical reactions. Electroactive conducting polymers including polypyrrole, polyaniline and polythiophene have been used to modify biosensors and bioelectronics [3,4]. In recent years, poly(3,4-ethylenedioxythiophene) (PEDOT) has been of considerable interest because of the possibility of producing a material with linear chains due to the blocking of the 3,4-positions of the thiophene ring [59]. This material lacks the presence of undesired ab(b0 ) and bb(b 0 ) couplings within the polymer backbone, and hence has high electrical conductivity and high electrochemical and thermal stability [10,11]. It belongs to a group of stable conducting polymers that are promising candidates for many technical applications [1215]. PEDOT has been electrochemically polymerized from

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aqueous solutions doped with dierent counterions, such as ClO4 [16], dodecyl sulfate [17] and poly(styrene sulfonate) (PSS) [18]. In this study, PEDOT was electrochemically synthesized on the surface of gold electrodes doped with one of its derivatives, sulfonatoalkoxy EDOT (S-EDOT). We have found that it is possible to deposit PEDOT/S-EDOT conducting lms on gold electrode sites. The lms have low impedance, high surface area and good charge capacity.

2. Experimental EDOT monomer (99%) was purchased from Bayer AG. S-EDOT was provided by Prof. John R. Reynolds of the University of Florida. Its chemical structure is shown in Scheme 1. PSS was purchased from Aldrich. Deionized water was used in the experiments. Neural probes were obtained from the Center for Neural Communications Technology (CNCT). The fabrication and structure of these devices has been reported elsewhere [19]. Features of the probes, including number and spacing of shanks and electrode sites can be customized to a given application. For this study, the probe was a singleshank electrode array with eight gold sites on its surface. The thickness of the probe was about 15 lm and the electrode site area was 1250 lm2. PEDOT/S-EDOT was deposited galvanostatically on the gold electrode sites of the neural probe. The current supply was a Gamry PC4/FAS1T Femtostat potentiostat/galvanostat/ZRA. The current was 6.0 nA, corresponding to a current density of 0.5 mA/cm2. The electrochemical apparatus was a 3-ml three-electrode cell. Individual electrodes, a platinum wire soldered at the bottom of the cell and a saturated calomel electrode (SCE) acted as the working electrode, the counter electrode and the reference electrode, respectively. The monomer solution containing 0.01 M EDOT and 0.05 M S-EDOT was purged with N2 for 5 min before electrochemical deposition. Reective Fourier transform infrared (FTIR) spectroscopy was used to characterize the chemical composition of the resultant conducting polymer lm. The instrument was a PerkinElmer Spectrum GX attached

to a PerkinElmer multiscope. The detector was cooled with liquid nitrogen before and during the experiments. The microscope accessory enabled the focusing of the IR beam on a very small area of the sample. In this experiment the aperture area was set at 35 35 lm2. The sample was scanned 100 times in the range from 4000 to 750 cm1. A Philips FEG XL30 scanning electron microscope (SEM) was used to study the surface morphology of PEDOT/S-EDOT lm with a voltage of 5 kV and a spot size of 3. A thin lm of gold/palladium was sputtered onto the probe using a Hummer-600 sputtering system to help reduce charging of the organic lm. The images were obtained using the secondary electron detector. The instrument for measuring the impedance was the same Gamry PC4/FAS1T Femtostat potentiostat/galvanostat/ZRA mentioned above. The system was operated under computer control using EIS software. A solution of 0.1 M phosphate buer solution (pH 7) was used as the electrolyte in a three-electrode cell. The range of frequency examined was from 1 to 105 Hz. Cyclic voltammetry (CV) was performed using the same Gamry instrument as for the deposition and impedance measurements. A scan rate of 10 mV/s was used and the potential on the working electrode was swept between 0.9 and 0.5 V vs. SCE.

3. Results and discussion PEDOT/PSS was deposited onto the surface of the electrodes of the neural probes [18]. One drawback of EDOT is its relatively poor solubility in water (0.01 M). Previous studies have shown that for thiophene, functionalization of the monomer by sulfonate groups increases its aqueous solubility [20]. First 0.05 M SEDOT was mixed with 0.1 M PSS in water and electrochemical polymerization was performed. Attempts to grow P(S-EDOT)/PSS on the working electrode were unsuccessful. No adherent lm was found on the gold electrode. It was reported that electropolymerization of the EDOT and S-EDOT mixture could be performed by repeated potential scans from 1.4 to 1.2 V [21]. In our study, PEDOT/S-EDOT lm was successfully deposited on the gold electrodes under galvanostatic conditions using a constant current density of 0.5 mA/cm2. In the process, the positive transient potential was between 0.8 and 0.9 V. The electropolymerization of the EDOT/S-EDOT mixtures produces homogeneous and strongly adherent water-insoluble lms. Considering the chemical structure of both monomers, S-EDOT is supposed to serve as a counterion in the process. Optical micrographs (Fig. 1) show that PEDOT/SEDOT is a conductive polymer that can be deposited electrochemically onto the gold electrodes of a neural

SO3Na O O O O O

S EDOT

S S EDOT

Scheme 1. Chemical structure of EDOT and S-EDOT.

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45

Fig. 1. Optical micrographs of neural probes with coated electrode sites.

probe. The lms were blueblack in color and the thickness increased with polymerization time. From the right image we can see clearly that the area of a site can be increased beyond the underlying gold site. The chemical composition of the conducting polymer lm on the electrodes was determined using reective microfocusing FTIR. Fig. 2 shows the IR spectrum of PEDOT/S-EDOT lm. The three peak absorptions at 1590, 1490, and 1400 cm1 can be assigned to the thiophene ring. The peak at 878 cm1 corresponds to the symmetric vibration of COC in a cyclic ether structure. The result conrms the existence of PEDOT, which is in agreement with previous studies [22]. The peak at 12201180 cm1 is a characteristic absorption of SO3. The spectrum indicated that the conducting lm was a combination of PEDOT and S-EDOT. It was conrmed that polypyrrole and its derivative functionalized with sulfonate groups could be represented as a copolymer with the composition of three pyrrole units to every pyrrole-sulfonate unit [23]. The main characteristic of the copolymer was its permanent ion-binding properties. On this basis, polymerization of the EDOT and SEDOT mixture may allow the formation of a copolymer

since the resulting polymer also exhibits permanent ionbinding behavior [21]. EDOT is the monomer mainly polymerized due to two facts: (1) steric hindrance upon radical coupling in S-EDOT; (2) the higher oxidation potential of S-EDOT. SEM was used to study the more detailed surface morphology of the PEDOT/S-EDOT lm coated on the electrode. Fig. 3 shows images of the PEDOT/SEDOT lm. The morphology was like a cauliower with many recesses in it. This apparently increases the surface area of the electrode. It has been reported that the actual surface area of a nodular polypyrrole lm was estimated to be 50 times greater than that of a smooth electrode of identical lateral dimensions [24]. The increase of surface area should result in the decrease of the impedance of the metal electrode. From SEM images, it is also seen that the surface morphology, and hence, the surface area of the conducting polymer deposited on the sites could be controlled by varying the deposition time. The impedance is a complex quantity dened as Z(x) = v(x)/I(x), where v(x) is the transform of an alternating potential signal applied to the system and I(x) is the transform of the alternating current signal that results. The impedance is a function of the frequency of the signal as well as the surface morphology. It is most

Fig. 2. FTIR spectrum of the PEDOT/S-EDOT coating.

Fig. 3. SEM images of PEDOT/S-EDOT lms as a function of time.

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generally represented as Z(x) = jZjeih. Its magnitude or modulus is jZj, and its phase angle is h. Both jZj and h may also be functions of the frequency. As the imaginary contribution increases, the phase angle increases. For a capacitor, the impedance is purely imaginary, the phase angle is 90 and the current is out of phase with the voltage by 90. However, in a resistor, the impedance is real, the current and the voltage are in phase, and the phase angle is zero. A large phase angle indicates that the impedance is predominantly capacitive, while for small angles, it is resistive. In this study, the impedance was measured over a range of frequencies from 1 to 105 Hz. The magnitude and phase angle information, which characterize the impedance, were measured directly. By using these data, we can obtain qualitative and quantitative information on the electrical properties of the coated and uncoated electrodes. Fig. 4 shows the impedance spectrum of a PEDOT/SEDOT coated electrode with the spectrum of an uncoated gold electrode as a control. Fig. 4(a) reveals that there

is a linear relationship between the magnitude of the impedance and the frequency for gold electrodes over this frequency range. It can be seen that the magnitude of either the bare gold or PEDOT/S-EDOT lm decreases with frequency. The magnitude of the PEDOT/S-EDOT lm was lower than that of the bare gold electrode over the whole frequency range from 1 to 105 Hz. At 1 kHz, which is the frequency characteristic of neural biological activity [25], the magnitude of a coated electrode was only 10.28 kX. It was nearly two orders of magnitude lower than that of bare gold (600 kX). This can be explained by the higher conductivity induced by the increased surface area of the polymer coating. From the phase plot (Fig. 4(b)) we can see that the phase angle for a PEDOT/S-EDOT coated electrode at 1 kHz was 10, while the phase angle of bare gold was about 80. From the discussion above, we know that the coated electrode is more resistive and the uncoated electrode is close to a pure capacitor. The roughness of the electrode surface resulted in a resistive component being added to the electrode-material system. From the Nyquist plot (Fig. 5) of the impedance spectroscopy, two distinct regions can be seen: a Warburgh diusion impedance in the high and medium frequency ranges and a nearly vertical line which represents a pure capacitive region in the low frequency range. It has been reported that conducting polymers grow on electrodes in a twostep process [26]. The initial growth results in a very dense and smooth lm. When it reaches a certain thickness, the polymer lm starts to become porous and fuzzy. The very thin dense lm provides a purely capacitive signal transport barrier, while the porous lm acts as a resistive component. The observation from the Nyquist plot is in agreement with previous study. The relationship between the magnitude of the impedance of the PEDOT/S-EDOT coating at a frequency of 1 kHz and deposition charge is shown in Fig. 6. The corresponding thickness is also shown in the gure.
200000

150000 -Z" /

100000

50000

0 0 50000 100000 Z' / 150000 200000

Fig. 4. Impedance spectroscopy of a bare gold electrode and PEDOT/ S-EDOT coated electrode: (a) magnitude and (b) phase angle.

Fig. 5. Nyquist plot of PEDOT/S-EDOT coating.

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From the curve, it is seen that the magnitude decreases sharply initially, as the deposition charge increases from 0 to 0.72 lC, then the rate of decrease slows down, reaching a minimum value of 10.28 kX at a charge of approximately 30 lC. After that, the magnitude gradually increases again. This trend correlates well with the lm surface morphology shown in Fig. 3. The surface starts as smooth bare gold. After some conducting polymer is deposited, the surface becomes very rough. Thus the surface area increases sharply. This evidently lowers the impedance of the electrode. With more material deposited, the surface becomes increasingly rougher. In this process many pores form and the lm reaches its highest eective roughness at a deposition charge of about 30 lC. This maximum surface area corresponds to the minimum impedance. Finally some pores are lled with more material being deposited, which is clearly seen in the right bottom SEM image. The roughness decreases, causing the impedance to increase, instead. This result corresponds well with our previous work [27]. CV provides information about the intrinsic redox reactions of the electrode material as the potential of the electrode is changed. The integration of I(t) within the cycled region gives the charge capacity of the lm, which was determined by how many mobile charges were moved in and out of the lm during the cycle. A higher interfacial area provides more sites with which ions can interact. Gold is inert and no redox reactions happen at the smooth gold electrode. The switching property of PEDOT/S-EDOT was conrmed in this study. Fig. 7 shows that within a single redox cycle, there are two peaks at potentials of 0.35 and 0.41 V vs. SCE.

Fig. 7. Cyclic voltammetry of PEDOT/S-EDOT coated electrode site.

The two values are indications of the oxidation and reduction reactions of PEDOT/S-EDOT, respectively. The redox reaction was accompanied by the movement of small cations in and out of the PEDOT/S-EDOT coating. The charge capacity of PEDOT/S-EDOT lm deposited using 18 lC on an area of 1250 lm2 was 4.67 lC, while it is almost 0 lC for bare gold. Thus the CV demonstrates the switching property of PEDOT/S-EDOT.

4. Conclusion Surface modication is needed on the electrode sites of the neural probes for better properties. Electron-rich conjugated polymers are especially useful for the formation of stable conducting polymer lms. Of these polymers, PEDOT and its derivatives are easily oxidized, stable conducting polymers that do not have the undesired ab(b 0 ) and bb(b 0 ) couplings often found in polypyrrole. PEDOT/S-EDOT was electrochemically polymerized on the electrode sites of neural probes. FTIR shows that the resultant coating is a combination of the two components. The deposited lm had rough surface morphology, and low impedance over a wide range of frequencies from 1 to 105 Hz. At 1 kHz the minimum magnitude of the impedance (10 kX at the deposition charge of 30 lC) was nearly two orders of magnitude lower than that of a bare gold electrode. The coated electrode was more resistive whereas the uncoated one was more capacitive. The switching properties of the PEDOT/S-EDOT lm were conrmed by CV. Within a single voltage sweep cycle, two peaks at 0.35 and 0.41 V appeared, indicating the oxidation and reduction reactions of the PEDOT/S-EDOT,

Film thickness / m 2 1000 4 6 8 10

|Z| at 1 kHz / k

100

10

1 0 10 20 30 Deposition charge / C 40 50

Fig. 6. Relationship between magnitude at 1 kHz and deposition charge.

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Y. Xiao et al. / Journal of Electroanalytical Chemistry 573 (2004) 4348 [9] V. Tsakova, S. Winkels, J.W. Schultze, Electrochim. Acta 46 (2000) 759. [10] G. Heywang, F. Jonas, Adv. Mater. 4 (1992) 117. [11] L.B. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, J.R. Reynolds, Adv. Mater. 12 (2000) 481. [12] F. Jonas, J.T. Morrison, Synth. Met. 85 (1997) 1397. [13] M. Granstrom, M. Berggren, O. Inganas, Science 267 (1995) 1479. [14] H. Yamato, M. Ohwa, W. Wernet, J. Electroanal. Chem. 397 (1995) 163. [15] J. Bobacka, Anal. Chem. 71 (1999) 4932. [16] J.C. Gustafsson, B. Liedberg, O. Inganas, Solid State Ionics 69 (1994) 145. [17] N. Sakmeche, S. Aeiyach, J.J. Aaron, M. Jouini, J.C. Lacroix, P.C. Lacaze, Langmuir 15 (1999) 2566. [18] X.T. Cui, D.C. Martin, Sens. Actuat. B: Chemical 89 (2003) 92. [19] J.F. Hetke, D.J. Anderson, K.D. Wise, In: Proceedings of the 18th Anuual International Conference of the IEEE Engineering in Medicine and Biology Society, Amsterdam, 1996. [20] A.O. Patil, Y. Ikenoue, F. Wudl, A.J. Heeger, J. Am. Chem. Soc. 109 (1987) 1858. [21] O. Stephan, P. Schottland, P.-Y.L. Gall, C. Chevrot, C. Mariet, M. Carrier, J. Electroanal. Chem. 443 (1998) 217. [22] C. Kvarnstrom, H. Neugebauer, S. Blomquist, H.J. Ahonen, J. Kankare, A. Ivaska, N.S. Sariciftci, Synth. Met. 101 (1999) 66. [23] S. Basak, K. Rajeshwar, Anal. Chem. 62 (1990) 1407. [24] L.L. Madsen, K. Carneiro, B.N. Zaba, A.E. Underhill, M.J. Van der Sluijs, Synth. Met. 4143 (1991) 2931. [25] S.W. Kuer, Sinauer Associates, Sunerland, MA, 1976. [26] T. Silk, Q. Hong, J. Tamm, R.G. Compton, Synth. Met. 93 (1998) 65. [27] Y.H. Xiao, J.Y. Yang, D.C. Martin, Poster in: 33rd Annual Neural Prosthesis Workshop, Bethesda, MD, October 2002.

respectively. The biocompatibility of the PEDOT/SEDOT coated neural microelectrode arrays with the surrounding tissue needs to be investigated in the future.

Acknowledgement This work was supported by the National Institute of Health NINDS-NO1-NS-1-2329 and the University of Michigan Center for Neural Communication Technology (CNCT). We thank Prof. John R. Reynolds for kindly providing the S-EDOT monomer.

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