Electrodepostion of PEDOT

Dorianne Ivonne Erazo Graduating Spring 2012 Summa Cum Laude Honors Bachelor of Science in Chemical Engineering

Abstract Among conductive polymers, PEDOT [poly(3,4ethylenedioxythiophene)], stands out for its excellent stability and high light transmissivity. Potential applications for the materials, especially in sensing applications, are generally discussed. PEDOT films on ITO on glass are developed through electrodeposition. The experiments are carried out using cyclic voltammetry and chronoamperometry with an acetonitrile solution containing LiClO4 ion. The samples are characterized through FTIR, a growth rate is determined, and sheet resistances are calculated. The films are found to be transparent and conductive.

Introduction to PEDOT PEDOT, poly(3,4ethylenedioxythiophene), has recently sparked much interest in the research field due to its evidently superior qualities over other polymers. Headlining these superior qualities are high stability, enhanced light transmission, processability, and simplicity of production [1]. Conductive polymers may be classified into two different categories: extrinsically conductive polymers and intrinsically conductive polymers. On one hand, extrinsically conductive polymers can involve a blend of conductive and nonconductive polymers, as well as metallic particles suspended in a polymer matrix [2]. They basically consist of highly conductive additives incorporated into polymer compounds, meaning that they are extrinsically enhanced to be conductive. Intrinsically conductive polymers, on the other hand, consist of a network of alternating single and double carbon bonds. This alternation of bonds produces conjugated -bonds that result in a conductive material. The molecule at hand, PEDOT, was developed by Bayer AG research laboratories as an intrinsically conductive polymer. Polymers in general offer some advantages over metallic or semiconducting materials. Combining the usual benefits of polymers with conductive qualities yields a product that is low in cost, lightweight, potentially moldable, and of course, highly conductive. Along with these advantages come some disadvantages, such as the fact that they are not as conductive as some metals, and precision in conductance is more limited. Furthermore, they are not as mechanically strong as some metals and may

Figure 1. Molecular structure for the PEDOT polymer.[13]

be damaged by scratching and abrasion [3]. While these specific properties are not up to par, they provide a range of potential points for improvement. PEDOT stands out as a material with high superiority over other polymers. The polymer backbone lacks the ability to form - linkages or - linkages, therefore the material is more regiochemically defined [4]. This is an ongoing problem for many other polymers being studied. An important characteristic of this polymer is high visible light transmissivity. PEDOT is a light blue color in its oxidized state, and a very dark color in its reduced state. Doping can create variable band gaps, ranging from 1.4 to 2.5 eV, resulting in a wide range of colors attainable [1]. High light transmissivity has already motivated PEDOTs industrial application anti-static coatings in photographic films, solar cells, and smart windows. Lastly, a major appealing quality of PEDOT is its inherent stability compared to other polymers. Films can be heated at 100C for up to 1000 hours without an appreciable change in conductivity [1]. They can also be stored under ambient conditions without affecting its stability. These two properties could mean low-cost shipping and storing conditions for potential PEDOT-based materials. Moreover, these films maintain their electrochemical activity over a wider range of pH than counterpart polymers. A study by Yamato, Ohrwa, and Wernet found that PEDOT films retained 89% of their electrochemical activity after polarization for 16 hours in solution with pH 7.5, versus only 5% found in polypyrrole. They also found similar favorable results for values as low as pH 6 [5]. The importance of this stability cannot be understated, as these are biologically relevant pH values, hinting at potential for medical applications utilizing this material. Furthermore, the polymer can be used in aqueous media without degradation, and exhibits higher resistance to fouling than other polymers [6]. These positive properties give rise to the wide array of potential applications for the material. The focus of this report will lie on prospective sensing technology utilizing the PEDOT polymer.

Sensing Applications Sensing applications utilize amperometric techniques to quantitatively analyze solutions. As mentioned before, biosensors are prospective sensors, but additional potential options include electronic tongues, and other anodic stripping sensors. PEDOT-based glucose biosensors have been researched by Kros, Hovell, Sommerdijk, and Nolte [7]. The basic biological interactions between glucose and the enzyme glucose oxidase (GOx) in the body shed some light onto potential sensor applications. Essentially, in the body, the enzyme GOx oxidizes glucose, gaining two electrons, and becoming reduced. Their study coats a track-etch membrane with PEDOT, and adsorbs the enzyme GOx onto the surface of the polymer coating. After the enzyme becomes reduced, it in turn reduces PEDOT, producing a current signal that can be used to measure concentrations of glucose. Their research concluded that glucose could be detected using potentials as low as 150 mV, with an average sensitivity for glucose of approximately 25 nA/mM, and a response time of less than 3 minutes. They also tested polypyrrole, and as highlighted before, PEDOTs stability as an electrode makes it more appealing than other polymers studied for the same purpose. It is therefore a likely candidate for long-term glucose measurement in medical devices. Another likely application involves the development of PEDOT-based electronic tongues. According to Martina, Ionescu, Pigani, Terzi, Ulrici, Zanardi and Seeber, an electronic tongue is defined as an analytical instrument that comprises a number of chemical sensors with partial selectivity for one class of analytes and only occasional specificity for precisely one analyte; such an instrument is capable of discriminating between complex samples without requiring knowledge of the compositions of the samples[8]. Their study tested and compared a PEDOT electrode to more commonly used Pt and Au electrodes by analyzing the responses after applying a DPV potential waveform. They conclude that all three electrodes are capable of differentiating between different kinds of fruit juices, as well as

different brand of the same kinds of juice. However, the PEDOT electrode offered the advantage of taking roughly half the time to conduct analysis compared to the other two electrodes. Furthermore, this electrode resulted in a higher degree of cross-selectivity, as it was best able to differentiate between the different brands of same juice. Another study tests PEDOTs potential as an electrode to operate as a quality control device in the wine industry [9]. It confirms that it has a sensitivity range reaching threshold limits for certain chemicals applicable to the trade, and highlights the fact that while it may be used as an electrode in a simple sensing arrangement, it could also be used as a single component in a larger sensing system comprised of other individual sensors, and enhance the system as whole. The last kind of amperometric sensor to be discussed involves the measurement of mercury in solution. Mercury and heavy metals in general are of high interest due to their possible toxicity, even at low concentrations. Research by Giannetto, Mori, Terzi, Zanardi and Seeber explores PEDOT-modified electrodes for use in the measurement of mercury [10]. Traditionally, Au electrodes are utilized, but they have the drawback that sometimes mercury can irreversibly diffuse into the electrode. Hence, the electrodes were modified to include the polymer. Some of the advantages for this specific application include anti-fouling properties, reproducibility of PEDOT films, and once again, high electrochemical stability after charge and discharge cycles. The group concludes that the modified electrodes are less expensive than the conventionally used gold electrodes, and have higher rapidity of analysis. These are a few examples of potential sensor applications for PEDOT films. It is evident throughout this compilation that conductivity, selectivity, processability, and stability are the most appealing properties provided by PEDOT, and they serve as a driving force for further development in the area of electrochemical sensors.

Therefore, this study serves as a preliminary assessment of PEDOT electrodeposition, with the goal of understanding the process and properties of generated films. As a long-term goal, these properties can be improved so that a material for the discussed potential applications may be developed. Theory of Electropolymerization of PEDOT PEDOT may be prepared by oxidative chemical polymerization from EDOT, electrochemical polymerization of the monomer, or transition metal-mediated coupling of dihalo derivatives of EDT [1]. The first, chemical polymerization, produces a dark, insoluble compound, and is usually performed using iron (III) chloride as the oxidizing agent, although other chemicals are also used for this purpose. The last method utilizes transition metal catalysts to prepare the polymer, and generally yields a material of low molecular weight. The method performed in this research is the oxidative electropolymerization of EDOT. It is favorable because of the general simplicity of the procedure, the fact that it requires small amounts of monomer, and because it entails short polymerization times. Some difficulties include that the polymers are made in small quantities, and some are insoluble, which can make certain techniques like NMR and size exclusion chromatography difficult [4]. The entire kinetics and chemistry of EDOT elecropolymerization is still under investigation, although there are some overall mechanics that are generally accepted by the scientific community [9]. Figure 2 depicts the process, beginning with the EDOT monomer in solution (Figure 2a). The first step is the oxidation of the EDOT monomer, as seen in Figure 2b. Then, the oxidized monomers diffuse toward the substrate-solution interface, and begin oligomerizing as shown in Figure 3c. This region becomes saturated with oligomers, which at that point begin depositing onto the surface of the substrate, forming growing nuclei that expand to eventually produce the desired film (Figure 2d).

It is at this point that there are alternative theories for the development of electrodeposited films. These nuclei can either form through progressive nucleation or instantaneous nucleation. In progressive nucleation, the nuclei deposit on the film following pseudo-first order kinetics until reaching steady state. In instantaneous nucleation, the maximum number of nuclei is formed just after the induction time. Furthermore, the manner in which the nuclei grow can vary. Metal deposition follows either 2D growth, where growth parallel to the substrate occurs at a higher rate than perpendicular growth, or it can also follow 3D growth, where the growth in both directions is similar. PEDOT films have been found to follow instantaneous 2D and 3D growth, the latter predominating at the beginning of the deposition, and the former at the final stages [9]. Experimental Procedure I.Film Electrodeposition The electrodeposition of PEDOT films was conducted under ambient conditions. A solution of 0.01 M EDOT and 0.1 M LiClO4 in acetonitrile was prepared. The electrochemical setup consisted of an ITO-covered glass film attached to a copper electrode, along with a carbon counter-electrode and a
Figure 2. The polymerization of EDOT begins by oxidation of the monomer (b). This is followed by oligomerization at the interface (c). The oligomers form growing nuceli on the surface of the substrate (d). Finally, the nuclei grow to form a PEDOT film.

saturated calomel reference electrode. A CV was performed using potentiostat

Versastat 3, seen in figure 3, giving a Current (A) 2.00E-03 1.50E-03 1.00E-03 5.00E-04 0.00E+00 0

PEDOT CV

potential value of 1.5 V. Constant potential electrodeposition was performed for amounts of time ranging from 20s to 300s. II.Nanowire electrodeposition

0.5

1.5

Potential (V)
Figure 3. CV for PEDOT electrodeposition. A constant potential of 1.5V was applied to subsequent experiments.

The experiments aiming to grow PEDOT nanotubes were conducted under the same conditions, with the exception that the substrate was an aluminum film, rather than ITO on glass. This is due to the fact that the nanowire-growing technique utilizes a template on an aluminum film. A standard CV was also performed for these experiments, yielding a similar potential of 1.5 V. This could be due to the fact that the CV assed the potential for the electrodeposition in non-template areas of the aluminum substrate. III.Carbon nanotube-PEDOT electrodeposition A suspension of carbon nanotubes on SDBS surfactant was used as the source of nanotubes. This experiment combined the nanotube suspension directly with the 0.01 EDOT/0.10 LiClO4 and performed the electrodeposition as described before. In order to determine the ratio of suspension to acetonitrile, a series of titrations were performed. By successively adding drops of acetonitrile to 25 mL SDBS solution, the amount of organic solvent at which the nanotubes began to aggregate was determined to be 6 mL. Thus, the electrodeposition was performed in a solution of 3:1 SDBS to acetonitrile. A copper electrode with aluminum substrate served as the working electrode, while a carbon counter electrode and a saturated calomel reference electrode were once again utilized. The CV was performed from -5 V to 8 V, and it showed an increasing trend throughout the entire range,

therefore, no specific potential for use in CP was observed. The solution foamed and there was very little deposition observed on the aluminum substrate. IV.PEDOT: PSS Spin Coating A sample of spin coated PEDOT: PSS was prepared in order to assess its conductive properties. The substrate used was once again ITO on glass. It was treated with O3 for 30 minutes, followed by spin coating with the PEDOT: PSS solution. As a last step, it was annealed at 300C for 1 hour. Results and Discussion The films created during electrodeposition were light blue in color, and would turn darker as the electrodeposition continued in time. Characterization of the PEDOT films was done through Fourier Transform Infrared Spectroscopy. Figure 4 shows the FTIR spectra obtained for a PEDOT film sample. Signals from 1527 to 1368 cm-1 are associated with the C=C bonds, peaks at 985, 844, and 688 cm-1 can be attributed to the C-S interaction in the thiophene ring, and peaks 1228 through 1051 cm-1 correspond to the ethylenedioxy group [12]. Based on this, it was concluded that PEDOT was the material sampled.

Figure 4. FTIR spectrum for PEDOT sample.

In order to obtain the deposition rate, three samples were performed at varying
7

Deposition Rate
6 Thickness (m) 5 4 3 2 1 0 0 100 200 Time (s)
Figure 5. Thickness trended over time highlights deposition rate.

times. The substrates were allowed to run for 20s, 100s and 300s. By observation, the 20s sample was very light blue and transparent, while the thicker samples were darker and opaque, as expected. The thickness of these samples was measured using a profilometer, and plotted versus time. Figure 5 shows the deposition rate for the analyzed PEDOT films. A
Sheet Resistance (m)

300

400

Sheet Resistance
2.50E-05 2.00E-05 1.50E-05 1.00E-05 5.00E-06 0.00E+00 5.8 1.9 0.831 0.12 Thickness (m) 100 s 20 s Spin Coated 300 s

rate of 1.08 m/min was calculated, confirming the relative speed of the reaction. In addition, resistance of the samples was measured using a four point probe and calculations for sheet resistances were obtained. As seen in Figure 6, sheet resistance decreased with the thickness of the sample, a

Figure 6. Sheet resistance increased with increasing thickness from the PEDOT samples. The spin coated sample consists of PEDOT:PSS.

common trend in electrodeposited films. It can be seen that the spin coated sample was both thinner and more conductive. This can be used as a benchmark standard to meet or surpass in future studies. It should be noted that the spin coated sample is doped with polystyrene sulfonate, a common practice to enhance the polymers conductivity and solubility.

Conclusions PEDOT films were able to be formed by electrodeposition. The films were shown to be conductive and transparent. A focus on expanding the sheet resistance of the films is important if this material is to be used for sensing or other applications. Sheet resistance can be potentially improved by doping, growing PEDOT nanowires, or developing films containing carbon nanotubes. These procedures are currently being investigated by this research group.

References 1. L. B. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, and J. R. Reynolds, Poly(3,4ethylenedioxythiophene) and its derivatives: past, present, and future, Advanced Materials,2000, vol. 12, no. 7, pp. 481494. 2. J.W. McBride, L. Lam, A review of conducting polymers in electrical contact applications. In,International Conference of Polymeric Materials in Power Engineering (ICPMPE),2007. 3. A. B. Strong, B. M. Lunt,Conductive Polymers: Why They Were Worth The Nobel Prize, 4. Groenendaal, L., Zotti, G., Aubert, P.-H., Waybright, S.M. and Reynolds, J.R., Electrochemistry of Poly(3,4-alkylenedioxythiophene) Derivatives, Adv. Mater., 2003, 15: 855879. doi: 10.1002/adma.200300376,. 5. Hitoshi Yamato, Masaki Ohwa, Wolfgang Wernet, Stability of polypyrrole and poly(3,4ethylenedioxythiophene) for biosensor application, Journal of Electroanalytical Chemistry,1995, vol. 397, no. 12, pp 163-170, ISSN 1572-6657, 10.1016/00220728(95)04156-8, . 6. S. Badhwar, Design,Fabrication and Characterisation of Organic electrochemical transistors: Chapter 2. Material aspects of PEDOT:PSS, 2006, Retrieved from 7. Kros, A., van Hvell, S. W. F. M., Sommerdijk, N. A. J. M. and Nolte, R. J. M. , Poly(3,4ethylenedioxythiophene)-Based Glucose Biosensors. Adv. Mater., 2001, 13: 15551557. doi: 10.1002/1521-4095(200110)13:20<1555::AID-ADMA1555>3.0.CO;2-7 8. Martina, V et al. Development of an electronic tongue based on a PEDOT-modified voltammetric sensor. Analytical and Bioanalytical Chemistry 387.6, 2007,: 2101-2110. 9. L. Pigani, A. Culetu, A. Ulrici, G. Foca, M. Vignali, R. Seeber, Pedot modified electrodes in amperometric sensing for analysis of red wine samples, Food Chemistry,2011, vol. 129, no. 1, pp. 226-233, ISSN 0308-8146, 10.1016/j.foodchem.2011.04.046. 10. Giannetto, M., Mori, G., Terzi, F., Zanardi, C. and Seeber, R. , Composite PEDOT/Au Nanoparticles Modified Electrodes for Determination of Mercury at Trace Levels by Anodic Stripping Voltammetry. Electroanalysis,2011, 23: 456462. doi: 10.1002/elan.201000469 11. H Randriamahazaka, V Nol, C Chevrot, Nucleation and growth of poly(3,4ethylenedioxythiophene) in acetonitrile on platinum under potentiostatic conditions, Journal of Electroanalytical Chemistry, 1999, vol. 472, no. 2, , Pages 103-111, ISSN 15726657, 10.1016/S0022-0728(99)00258-2. 12. Selvaganesh, S. Vinod and Mathiyarasu, J. and Phani, K. L. N. and Yegnaraman, V., Chemical synthesis of PEDOT-Au nanocomposite. NANOSCALE RESEARCH LETTERS, 2007,2 (11). pp. 546-549. 13. Polymer Synthesis Could Aid Future Electronics, Lab Spaces, 2010