Improved PEDOT Conductivity via Suppression of Crystallite Formation in Fe(III) Tosylate During Vapor Phase Polymerization

Zuber, Kamil; Fabretto, Manrico; Hall, Colin; Murphy, Peter

doi:10.1002/marc.200800325

Cited by 88 publications

(72 citation statements)

References 23 publications

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“…18 Electrochemical polymerization only allows the coating of conductive substrates and can produce nonuniform films for larger areas. 19 VPP offers a viable alternative to other methods of preparing highly conductive PEDOT films. A conductive polymer film is formed by a chemical reaction between an oxidant and EDOT obtained from vapor phase.…”

mentioning

confidence: 99%

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Metsik

Saal

Mäeorg

et al. 2014

J Polym Sci B Polym Phys

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Transparent [90% transmittance at 550 nm at a sheet resistance (R s ) of 279 X sq 21 ] poly(3,4-ethylenedioxythiophene) (PEDOT) films with electrical conductivities up to 1354 S cm 21 are prepared using base-inhibited vapor phase polymerization at atmospheric pressure. The influence of reaction conditions, such as temperature and growth time, on the film formation is investigated. A simple and convenient twoelectrode method is used for the in situ measurement of resistance, enabling to investigate the growth mechanism of polymer films and the influence of different parameters (relative humidity and the amount of oxidant) on the film growth. Low humidity exerts a detrimental effect on film growth and conductivity. In situ R s measurements suggest that a large structural change occurs upon washing the PEDOT-oxidant film.

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mentioning

confidence: 99%

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Metsik

Saal

Mäeorg

et al. 2014

J Polym Sci B Polym Phys

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“…Another study investigating both the effects of humidity and PEG-ran-PPG as an additive found an optimal relative humidity of 35%, yielding the highest conductivity film, as shown in Figure 12. 83 A similar dependence on the presence of water vapor during polymerization was seen in depositing PPy. 86 Fabretto et al suggest that the water is acting as an effective proton scavenger allowing polymerization to proceed.…”

Section: Reviewmentioning

confidence: 58%

“…55,82 In addition to controlling the humidity in the VPP chamber, incorporation of a surfactant such as poly(ethylene glycol)-ran-poly(propylene glycol) (PEG-ran-PPG) to the oxidant solution also inhibits the adverse effects of water absorption and prevents the oxidant from forming crystallite domains during the VPP process resulting in a significant increase in the conductivity from 84 S cm À1 to 528 S cm À1 . 83,84 It is believed that PEG-ran-PPG co-ordinates to the Fe 3þ ions in the oxidant iron(III) tosylate and reduces the effective reactivity of the oxidant which reduces the rate of polymerization leading to increased conductivity as shown in Figure 11. 84 Further studies revealed that the surfactant can potentially replace the weak bases such as pyridine and imidazole in reducing the apparent reactivity of the oxidant, thus eliminating the problems associated with volatility of low molecular weight organic bases.…”

Section: Reviewmentioning

confidence: 99%

Vapor phase oxidative synthesis of conjugated polymers and applications

Bhattacharyya

Howden

Borrelli

et al. 2012

J Polym Sci B Polym Phys

113

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Since their discovery, electrically conductive polymers have gained immense interest both in the fields of basic and applied research. Despite their vast potential in the fabrication of efficient, flexible, and low-cost electronic and optoelectronic devices, they are often difficult to process by wetchemical methods due to their very low to poor solubility in organic solvents. The use of vapor-based synthetic routes, in which conductive polymers can be synthesized and deposited as a thin film directly on a substrate from the vapor phase, provides many unique advantages. This article discusses oxidative vapor deposition processes, primarily vapor phase polymerization and oxidative chemical vapor deposition, of conjugated polymers and their applications. The mild operating conditions (near room temperature processing) allow conformal and functional coatings of conjugated polymers on delicate substrates.

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“…The evaporation of residual butanol from the dot exposes the hygroscopic Fe(III) tosylate which, on cooling, absorbs water from the atmosphere to form large (400−600 nm high) crystals. 11 A dot of oxidant ink which has been exposed to EDOT monomer in the VPP chamber ( Figure 3G−I) exhibits a nodular morphology and little, if any, crystallization. In this case the oxidant has polymerized the monomer and the tosylate anion has become incorporated in the resulting PEDOT as dopant.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

et al. 2012

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Some of the most exciting recent advances in conducting polymer synthesis have centered around the method of vapor phase polymerization (VPP) of thin films. However, it is not known whether the VPP process can proceed using significantly reduced volumes of oxidant and therefore be implemented as part of nanolithography approach. Here, we present a strategy for submicrometer scale patterning of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) via in situ VPP. Attolitre (10 -18 L) volumes of oxidant "ink" are controllably deposited using dip-pen nanolithography (DPN). DPN patterning of the oxidant ink is facilitated by the incorporation of an amphiphilic block copolymer thickener, an additive that also assists with stabilization of the oxidant. When exposed to EDOT monomer in a VPP chamber, each deposited feature localizes the synthesis of conducting PEDOT structures of several micrometers down to 250 nm in width. PEDOT patterns are characterized by atomic force microscopy (AFM), conductive AFM, two probe electrical measurement, and micro-Raman spectroscopy, evidencing in situ vapor phase synthesis of conducting polymer at a scale (picogram) which is much smaller than that previously reported. Although the process of VPP on this scale was achieved, we highlight some of the challenges that need to be overcome to make this approach feasible in an applied setting. ABSTRACT: Some of the most exciting recent advances in conducting polymer synthesis have centered around the method of vapor phase polymerization (VPP) of thin films. However, it is not known whether the VPP process can proceed using significantly reduced volumes of oxidant and therefore be implemented as part of nanolithography approach. Here, we present a strategy for submicrometer scale patterning of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) via in situ VPP. Attolitre (10 −18 L) volumes of oxidant "ink" are controllably deposited using dip-pen nanolithography (DPN). DPN patterning of the oxidant ink is facilitated by the incorporation of an amphiphilic block copolymer thickener, an additive that also assists with stabilization of the oxidant. When exposed to EDOT monomer in a VPP chamber, each deposited feature localizes the synthesis of conducting PEDOT structures of several micrometers down to 250 nm in width. PEDOT patterns are characterized by atomic force microscopy (AFM), conductive AFM, two probe electrical measurement, and micro-Raman spectroscopy, evidencing in situ vapor phase synthesis of conducting polymer at a scale (picogram) which is much smaller than that previously reported. Although the process of VPP on this scale was achieved, we highlight some of the challenges that need to be overcome to make this approach feasible in an applied setting.

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Improved PEDOT Conductivity via Suppression of Crystallite Formation in Fe(III) Tosylate During Vapor Phase Polymerization

Cited by 88 publications

References 23 publications

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Vapor phase oxidative synthesis of conjugated polymers and applications

Vapor Phase Polymerization of EDOT from Submicrometer Scale Oxidant Patterned by Dip-Pen Nanolithography

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