Electropolymerization and doping/dedoping properties of polyaniline thin films as studied by electrochemical-surface plasmon spectroscopy and by the quartz crystal microbalance

Baba, Akira; Tian, Shichao; Stefani, Fernando D.; Xia, Chao; Wang, ‪Zhehui; Advincula, Rigoberto C.; Johannsmann, Diethelm; Knoll, Wolfgang

doi:10.1016/j.jelechem.2003.08.012

Cited by 151 publications

(123 citation statements)

References 47 publications

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“…Polyaniline is a conducting polymer that has attracted considerable research interest [1][2][3][4][5][6], notably with regard to its chemical [7], electrochemical [8,9] and optical [4,9] properties. In pursuit of understanding these properties based on the underlying elementary processes, detailed studies have been reported of various features of redox switching dynamics [3,8,[10][11][12][13][14] and polymer structure [3,10,[15][16][17].…”

Section: Introductionmentioning

confidence: 99%

“…Based on SEM images [3,16] and electrochemical quartz crystal microbalance (EQCM) data [3,10,16] of polyaniline films, it has been proposed that anions fall into two categories. Empirically, so-called "class 1" anions (BF 4 -, ClO 4 -and CF 3 CO 2 -) lead to compact films, while so-called "class 2" anions (SO 4 2-, NO 3 -and Cl -) lead to more open films [16]; however, the underlying rationale for this distinction is not clear. Correlation of EQCM and SEM morphological data could in principle be helpful in this respect, but the fact that the former technique is applied in situ and the latter ex situ means that comparisons are not necessarily straightforward.…”

Section: Introductionmentioning

confidence: 99%

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The effect of anion identity on the viscoelastic properties of polyaniline films during electrochemical film deposition and redox cycling

Mohamoud

Hillman

2007

Electrochimica Acta

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Acoustic admittance measurements at thickness shear mode resonators were used to determine shear moduli for polyaniline films during their potentiodynamic electrodeposition and subsequent redox cycling in aqueous background electrolyte. Data were acquired for films doped with perchlorate, sulphate or chloride anion. For all media, film shear moduli increased progressively with film thickness, from values consistent with a diffuse fluid-like layer to values typical of a viscoelastic material. At any given thickness, both the storage and loss moduli were largest in perchlorate medium; values in chloride and sulphate media were similar to each other, but smaller than in perchlorate. These measures of polymer dynamics are consistent with a previous classification of polyaniline film behaviour, in which perchlorate-doped films are viewed as compact while chlorideand sulphate-doped films are viewed as more open. In monomer-free background electrolyte solution, both film shear modulus components for all anions increased modestly upon film oxidation. Despite some hysteresis on the timescale of slow scan voltammetry, these variations were chemically reversible. Based on measurements involving deposition from chloride medium and transfer to sulphate medium, film shear moduli respond promptly to changes in dopant identity; this is consistent with rapid redox-driven exchange of anions with the bathing electrolyte.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The effect of anion identity on the viscoelastic properties of polyaniline films during electrochemical film deposition and redox cycling

Mohamoud

Hillman

2007

Electrochimica Acta

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“…This increase in minimum angle can be used to estimate the polymer thickness using the refractive index of the reduced film (n ) 1.6), giving a film thickness of ∼2.2 nm. 31,49 The behavior of this thin polymer film can be analyzed using both electrochemical and SPR measurements. Under acidic conditions, poly(aniline) can be readily transformed between its reduced and oxidized state via potential cycling.…”

Section: Resultsmentioning

confidence: 99%

“…49 Notably, the SPR response of thicker poly(aniline) films is typically dominated by the increase in conductivity and its impact on the imaginary part of the polymer's refractive index. 27,30,31 Although these results give a quantitative picture of the film behavior during redox switching, SPR angle spread images can provide a more rapid signature of the differences. Figure 4C,D depicts two different angle spread SPR images of poly(aniline)-coated electrodes.…”

Section: Resultsmentioning

confidence: 99%

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Combined Electrochemical Surface Plasmon Resonance for Angle Spread Imaging of Multielement Electrode Arrays

Choi

Hillier

2010

Anal. Chem.

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A surface plasmon resonance imaging system combined with a multielement electrode array is described. An optical system with shaping optics is used to direct a wedge of light onto a gold-coated sample. The reflected light is detected in the form of an angle-spread image of the surface, with one direction denoting a variable incident angle and the other showing a span of locations along one lateral direction of the sample surface. At the proper incident angle, the angle-spread image shows the complete surface plasmon resonance curve over a span of locations on the surface. This imaging system is combined with a sample configuration consisting of a series of gold microelectrode bands, each with independent electrochemical control. In solution, this system can be used to perform high-throughput and dynamic electrochemical experiments. Simultaneous measurement of electrochemical and surface plasmon resonance can be quantitatively performed on each of the electrode surfaces either by holding each electrode at a different potential value or by scanning the applied potential. The sensitivity of this configuration is demonstrated by monitoring oxide formation and removal at a gold electrode in an aqueous electrolyte. A second example, with the use of a thin poly(aniline) coating, illustrates the ability to monitor film changes, including thickness, dielectric properties, and associated electrochemically induced polymer oxidation/reduction on multiple electrodes. This represents a simple and compact method for combining the sensitivity of surface plasmon resonance into an array-based, high-throughput electrochemical system.

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Functional Layer‐By‐Layer Polyelectrolytes: Assembly Strategies, Characterization, and Selected Applications

Estillore

Knoll

Advincula

2012

Ionic Interactions in Natural and Synthetic Macromolecules

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Electropolymerization and doping/dedoping properties of polyaniline thin films as studied by electrochemical-surface plasmon spectroscopy and by the quartz crystal microbalance

Cited by 151 publications

References 47 publications

The effect of anion identity on the viscoelastic properties of polyaniline films during electrochemical film deposition and redox cycling

The effect of anion identity on the viscoelastic properties of polyaniline films during electrochemical film deposition and redox cycling

Combined Electrochemical Surface Plasmon Resonance for Angle Spread Imaging of Multielement Electrode Arrays

Functional Layer‐By‐Layer Polyelectrolytes: Assembly Strategies, Characterization, and Selected Applications

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