Conducting polymer film, measured

The electrochemistry of a polymer-modified electrode is determined by a combination of thermodynamics and the kinetics of charge-transfer and transport processes. Thermodynamic aspects are highlighted by cyclic voltammetry, while kinetic aspects are best studied by other methods. These methods will be introduced here, with the emphasis on how they are used to measure the rates of electron and ion transport in conducting polymer films. Charge transport in electroactive films in general has recently been reviewed elsewhere.9,11... 

Impedance spectroscopy is best suited for the measurement of electronic conductivities in the range 10 -7to 10 2S cm 1.145 In principle, it is perhaps the best method for this range, but it is often difficult to interpret impedance data for conducting polymer films. The charge-transfer resistance can make measurements of bulk film resistances inaccurate,145 and it is often difficult to distinguish between the film s ionic and electronic resistances.144 This is even more of a problem with chronoamperometry146 and chronopotentiometry,147 so that these methods are best avoided. 

The results from EQCM studies on conducting polymer films can be ambiguous because the measured mass change results from a combination of independent ion transport, coupled ion transport (i.e., salt transport), and solvent transport. In addition, changes in the viscoelasticity of the films can cause apparent mass changes. The latter problem can be minimized by checking the frequency response of the EQCM,174 while the various mass transport components can be separated by careful data analysis.175,176... 

POEA), a conducting polymer. The measurements were carried out using both solution and polymer films deposited by the self-assembly technique (Paterno and Mattoso, 2001). Figure 16.21 presents the Raman spectra of FA, POEA, and POEA/ FA complexes in different concentrations of FA. 

Hillman et al. measured the quartz crystal impedance to determine changes in rigidity, swelling and ionic exchange in conducting polymer films [57, 58] and have also used dynamic quartz crystal impedance of modified electrodes during film growth and redox conversion [57] by qualitative analysis of the acoustic admittance-frequency peak width. 

If the chronoamperometric response of a - polymer-modified electrode is measured alone - in contact with inert - supporting electrolyte - Cottrell-type response can be obtained usually for thick films only, because at short times (f < 0.1-1 ms) the potential is not established while, at longer times (t > 10-100 ms), the finite diffusion conditions will prevail and / exponentially decreases with time. Another complication that may arise is the dependence of D on the potential in the case of - conducting polymer films [vi]. 

Given the nature of the polymer and the conduction pathway, a simple homogeneous model cannot be applied to thin conducting polymer film-electrolyte systems [27,28,31]. For thin films (< lOOnm) with pore sizes estimated to range from 1 to 4 nm, the porous surface-electrolyte interface will dominate the electrical and physical properties of the sensor. Since the oxidation of the porous surface occurs first, the interface properties play a major role in determining device response. To make use of this information for the immunosensor response, the appropriate measurement frequency must be chosen to discriminate between bulk and interface phenomena. To determine the optimum frequency to probe the interface, the admittance spectra of the conducting polymer films in the frequency range of interest are required. 

The first subdiscipline of chemistry in which the QCM was widely applied was electrochemistry. In 1992 Buttry and Ward published a review entitled Measurement of interfacial processes at electrode surfaces with the electrochemical quartz crystal microbalance , with 133 references [8]. This is the most widely cited paper on quartz crystal microbalances. After presenting the basic principles of AT-cut quartz resonators, the authors discuss the experimental aspects and relation of electrochemical parameters to QCM frequency changes. In their review of the investigation of thin films, they discuss electrodeposition of metals, dissolution of metal films, electrovalency measurements of anion adsorption, hydrogen absorption in metal films, bubble formation, and self-assembled monolayers. The review concludes with a brief section on redox and conducting polymer films. 

Cai, H., Xu, Y, He, P.-G., and Fang, Y.-Z. (2003). Indicator free DNA hybridization detection by impedance measurement based on the DNA-doped conducting polymer film formed on the carbon nanotube modified electrode. Electroanalysis, 15, pp. 1864-1870. 

Thus, a potential-dependent smooth background in IR spectra can be due to modulation of concentration/population of free carries and surface states. In contrast to common capacitance measurements, IR spectra of free carrier can provide information on the space charge capacitance of the semiconductor electrode under accumulation as well as under depletion conditions, without interference from the surface state capacitance. The DA-potential plots under depletion conditions allow measurements of the flat-band potential, while absorption of charge carriers in conducting polymer films can be used for estimating the film conductivity. It is also possible to follow the filling of surface states and relate these energy levels to the chemical composition of the interface. 

Piezoelectric microgravimetry in conjimction with electrochemical measurements is a very powerful but relatively simple and cheap techrrique, and so within the last twenty years it has become one of the most popular hyphenated techrriques for studying the formation of conducting polymer films and ion and solvent exchange processes that occur during their redox reactions, which provide valtrable information about the reaction mechanism [6-9,43,70,89,90,98,107,151,153,154,156-166,168-232],... 

Bund A, Schneider M (2002) Characterization of the viscoelasticity and surface roughness of electrochem-ically prepared conducting polymer films by impedance measurements at quartz crystals. J Electrochem Soc 149(9) E331-E339... 

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