CHAPTER 2

MATERIAL ASPECTS OF PEDOT: PSS

2.1 INTRODUCTION

During the second half of the 1980s, scientists at the Bayer AG research laboratories in Germany developed a new polythiophene derivative, poly (3, 4 ethylenedioxythiophene), having the backbone structure shown below.

Figure 2.1 shows the molecular structure of PEDOT This polymer, often abbreviated, as PEDOT was initially developed to give a soluble was initially developed to give a soluble conducting polymer that lacked the presence of undesired , and , couplings within the polymer backbone. Prepared using standard oxidative chemical or electrochemical polymerization methods, PEDOT was initially found to be an insoluble polymer, yet exhibited some very interesting properties. In addition to a very high conductivity (ca. 200 S/cm), PEDOT was found to be almost transparent in thin, oxidized state.

Figure 2.2 shows the molecular structure of PSSH and PSS-Na+

The solubility problem was subsequently circumvented by using a water-soluble polyelectrolyte, poly (styrene sulfonic acid) (PSS), as the charge-balancing dopant during polymerization to yield PEDOT: PSS.

Figure 2.3 shows the molecular structure of PEDOT: PSS

This combination yields a water-soluble polyelectrolyte with a good film forming properties, high conductivity (ca. 10 S/cm), high visible light transmissivity, and excellent stability. Films of PEDOT: PSS can be heated in air at 100 degree Celsius for over 1000 hours with only a minimal change in conductivity. With this new system, now known under its commercial name BAYTRON P (P stands for polymer), Bayer researchers have been able to develop several applications. Although initially used as an antistatic coating in photographic films from AGFA, several new applications have been implemented over the past few years (e.g., electrode material in capacitors, material for through-hole plating of printed circuit boards), and more are expected. Driven by the properties and utility of PEDOT: PSS, a number of research groups have entered the area of PEDOT chemistry over the past decade. The latter has resulted in an exponential increase in the number of patents and journal publications. [2-3] Both PEDOT and PSS contain one sulfur atom per repeat unit. The sulfur atom in PEDOT is within the thiophene ring, whereas in PSS, it is included in the sulfonate moiety. [32]

2.2 SYNTHESIS OF PEDOT

The synthesis of PEDOT can be divided into three different polymerization reactions:

2.2.1 OXIDATIVE CHEMICAL POLYMERIZATION OF THE EDOT BASED MONOMERS

Chemical polymerization of EDOT derivatives can be carried out using several methods and oxidants. The classical method employs oxidizing agents such as FeCl3 or Fe (OTs)3 . The most practically useful, polymerization method for EDOT utilizes the polymerization of EDOT in an aqueous polyelectrolyte (most commonly known as PSS) solution using Na2S2O8 as the oxidizing agent. Carrying out this reaction at room temperature, results in a dark blue, aqueous PEDOT/PSS.

2.2.2 ELECTROCHEMICAL POLYMERIZATION OF EDOT DERIVATIVES

Another especially useful polymerization method utilizes electrochemical oxidation of the electron-rich EDOT based monomers. This method is important because it requires only small amounts of monomer, short polymerization times, and can yield both electrode-supported and freestanding films. In the case of EDOT itself, electrochemical polymerization results in the formation of a highly transmissive sky-blue, doped PEDOT film at the anode.

2.2.3

TRANSITION

METAL-MEDIATED

COUPLING

OF

DIHALO

DERIVATIVES OF EDOT

Many thiophenebased polymers have been prepared over the years using transition metal-catalysed coupling of activated organometallic derivatives. This method yields materials with low molecular weight.

2.3 ELECTROCHEMISTRY OF PEDOT: PSS

The combination of an especially low oxidation potential and a relatively low band gap gives PEDOT some unique electrochemical and spectroscopic properties not accessible in other polymers. As band gap is located at the transition between the visible and near-IR regions of the spectrum, PEDOT is strongly cathodically coloring and transmissive to visible light, sky blue transparent, in the doped and conducting state (oxidized state).

Figure 2.4 shows the UV Vis spectra of PEDOT films in reduced (solid line) and oxidized (dashed line) state. The change of the redox state leads to a change in the electronic structure, which is observed as an optical color transition to dark blue. It is for this reason, PEDOT: PSS is called an electro chromic polymer. The low oxidation potential of PEDOT and the resulting ambient stability arises because of the high HOMO (highest occupied molecular orbital) level. HOMO level is analogous to the term valence band, associated with inorganic semiconductors, and used to imply a lower set of energy levels, completely filled with electrons. Similarly, LOMO (lowest occupied molecular orbital) level can be compared to the conduction band, a term used to explain a vacant or partially occupied set of many closely spaced electronic levels in which the electrons are free to move. The difference between the HOMO level and the LOMO level is referred as the band gap of the material.

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2.4 CONDUCTIVITY ENHANCEMENT OF PEDOT: PSS

The conductivity of PEDOT: PSS film can be enhanced by more than two orders of magnitude by adding compounds with two or more polar groups, like ethylene glycol, into an aqueous solution of PEDOT: PSS.The additive induces a conformational change in the PEDOT chains in the PEDOT: PSS film.

Figure 2.5 shows the conformational change in PEDOT after treatment with additive.

Both coil and linear or expandedcoil conformations exist in untreated PEDOT: PSS films, whereas the linear or expanded coil conformation becomes dominant in highconductivity PEDOT: PSS films. This conformational change results in an increase in the intrachain and interchain charge-carrier mobility, so that the conductivity is enhanced. [4]

2.5 CHARGE TRANSPORT IN THE CONDUCTING POLYMER PEDOT: PSS

Conducting polymers have rarely been produced in a form ordered enough to exhibit a small positive temperature coefficient of resistivity. This so-called metallic behavior is normally not seen in the transport properties of as-grown conducting polymers like polypyrroles, polythiphenes, or polyanilines where the negative temperature coefficient of the resistivity is generally attributed to hopping.

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The (T), representing the temperature dependent conductivity of spin coated PEDOT: PSS thin films can be described by (T) = exp [-(To/T) ]

where is the conducting prefactor, To is the characteristic temperature dependent on the pH and is an exponent that is related to the transport process. This temperature dependence is characteristic of strongly disordered, inhomogeneous systems. The temperature variation of the conductivity log [ (T)], is plotted as a function of the power of the temperature, T- , and the appropriate value which straightens out the curve is considered to provide information about the conducting mechanism. A value close to is attributed to variable range hopping and a value close is generally attributed to the presence of a Coulomb gap, either in the homogenous system of localized interacting electrons or in the form of a charging energy in a granular metal-like system. The charge transport mechanism in the case of PEDOT: PSS can be generally explained within the framework of the charging-energy limited tunneling model, originally proposed for highly disordered conducting polymers. In this model, conduction is supposed to proceed from tunneling between small conducting grains separated by insulating barriers. This model is an extension of Shengs model of granular metals; it focuses on the disorder present in the polymer and the polaronic ground state characteristic in many conducting polymers. According to this model, the conducting clusters are highly doped polaronic islands generated by heterogeneities in the doping distribution. The dopant centers act as bridges between neighboring chains and therefore improve the charge carrier transport. [29-31]

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2.6 MORPHOLOGY AND ANISOTROPY OF PEDOT: PSS

Very little is known about the molecular structure and the surface and bulk morphology of PEDOT: PSS. The structure and morphology of thin films are not necessarily the same as that of bulk material. For PEDOT, thin spincast and bulk solution-cast films show very different kinds of orientation, although they have the same basic crystalline structure. Grazingincidence X-ray diffraction studies have shown that the dopant ions, form distinct planes, which alternate with stacks or lamellae of polymer chains. The material is very anisotropic, with the planes of the dopants and of the stacks of polymer chains parallel to the substrate. It is in a paracrystalline state, with small size of the individual paracrysatalline regions. [28] This model corroborates well with the strong optical anisotropy observed. Despite the observed anisotropy in the optical response, possible anisotropies in the conductivity were systematically addressed, only until recently. Multimodal AFM studies carried out to map the local charge transfer properties in correlation to the molecular superstructure of the polymer blend show that efficient charge injection occurs in regions where the lamellar edges are exposed to the probe. Charge mobilitys are considerably higher along the polymer lamellae, as compared to normal mobilities for PEDOT.In regions where the AFM tip has access to orbital that belong to a lamellar edge, efficient charge transport occurs. Therefore, high currents are observed. On the contrary, when the AFM tip is scanning on top of intact lamellae, the high inter-sheet barrier, limits the transport. The interlamellar distance is estimated to be 3nm. [26]

Figure 2.6 shows the lamellar structure of PEDOT: PSS blend

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These studies suggest that the charge transport perpendicular to the substrate is dominated by space charge effects, in striking contrast to the hopping transport observed parallel to the substrate. Recent studies combine scanning probe microscopy with macroscopic temperature dependent conductivity measurements to build a full 3 Dimensional morphological model that explains the observed anisotropic conductivity of spin coated PEDOT: PSS thin films. The vertical conductivity that is perpendicular to the substrate can be up to three orders of magnitude lower than the lateral conductivity in the plane of the film. Surface Tunneling Microscopy shows that the PEDOT: PSS films have a granular morphology, with a typical grain size of about 10-25nm.The low surface roughness of approximately 1.75nm implies that the grains actually have the shape of flattened balls, or pancake-like structures. The transformation of spherical particles in solution to pancakes in thin films is most likely the result of spin casting procedure, during which the evaporating water causes the thickness to shrink while the film remains continuous in the lateral direction. [27]

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