Morphology and Doping Level of Electropolymerized Biselenophene-Flanked 3, 4- Ethylenedioxythiophene Polymer: Effect of Solvents and Electrolytes. (20th February 2016)

• Record Type: Journal Article
• Authors: Agrawal, Vikash; Shahjad, ; Bhardwaj, Dinesh; Bhargav, Ranoo; Sharma, Gauri Datt; Bhardwaj, Ramil Kumar; Patra, Asit; Chand, Suresh
• Is Part Of: Electrochimica acta. Volume 192(2016)
• Page Start: 52
• Page End: 60
• Publication Date: 2016-02-20
• Subjects: Biselenophene-flanked EDOT -- Electropolymerization -- Morphology & Doping-dedoping -- Optoelectronic properties -- Computational; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2016.01.157
• Languages: English
• ISSNs: 0013-4686

Abstract

Highlights: Biselenophene-flanked 3, 4-ethylenedioxythiophene polymer films were obtained by electrochemical polymerization. Supporting electrolyte has significant effect on the doping level, whereas electropolymerized solvent has a major effect on morphology of the polymer films. Optoelectronic properties and morphology of the electropolymerized films were studied. Density functional theory (DFT) calculation has been made for optoelectronic properties. Abstract: Biselenophene-flanked 3, 4-ethylenedioxythiophene (EDOT) based polymer films were obtained by electrochemical polymerization. The effects of polymerization conditions such as supporting electrolytes and solvents on doping level, optical property and morphology of the polymer films were systematically studied. Interestingly, we found that polymer prepared by using different supporting electrolytes (TBAPF6, TBABF4 and TBAClO4 ) has significant effects on the doping level of the polymer films, whereas electropolymerized solvents (acetonitrile and dichloromethane) has no such effects on doping level. The polymer films show reversible dedoping and doping behavior upon treatment with hydrazine hydrate and iodine respectively. Biselenophene-flanked EDOT polymer shows a band gap of about 1.6 eV which is comparable to poly(3, 4- ethylenedioxythiophene) (PEDOT) and parent polyselenophene, whereas fine-tuning of HOMO and LUMO energy levels has been found. In contrast, we observed that electropolymerized solvent has a major effect on morphology of the polymer films, while supporting electrolyte has very minor effects on the morphology. The surface morphologies of the polymer films were characterized by scanning electron microscope (SEM) and atomic force microscope (AFM) techniques. We also present an efficient synthesis of bisthiophene-flanked bridged EDOT (ETTE), and biselenophene-flanked bridged EDOT (ESeSeE), and their electrochemical polymerization, characterizations and throughout comparison where applicable. A density functional theory (DFT) calculation of the corresponding polymers and a comparison with polythiophene (PT), polyselenophene (PSe), PEDOT and EDOT- based copolymers (PETE and PESeE) has been made.