Effect of Ion-Chelating Chain Lengths in Thiophene-Based Monomers on in Situ Photoelectrochemical Polymerization and Photovoltaic Performances

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Department of Chemical Engineering, Pohang University of Science and Technology, San31, Nam-gu, Pohang, Kyoungbuk 790-780, Korea
*E-mail: [email protected]. Fax: + 82-54-279-8298. Tel: 82-54-279-2394.
Cite this: ACS Appl. Mater. Interfaces 2015, 7, 21, 11482–11489
Publication Date (Web):May 15, 2015
Copyright © 2015 American Chemical Society
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We synthesized thiophene-based monomers (bis-EDOTs) with different ethylene glycol oligomer (EGO) lengths (TBO3, TBO4, and TBO5) and investigated their polymerization characteristics during photoelectrochemical polymerization (PEP) at the surfaces of dye (D205)-sensitized TiO2 nanocrystalline particles. During the PEP reaction, monomers were expected to diffuse toward neighboring dyes through the growing polymer layers to enable continuous chain growth. We found that the less bulky monomer (TBO3) formed a more compact polymer layer with a high molecular weight. Its diffusion to the active sites through the resulting growing polymer layer was, therefore, limited. We deployed layers of the polymers (PTBO3, PTBO4, and PTBO5) in iodine-free solid-state hybrid solar cells to investigate the lithium ion chelating properties of the polymers as a function of the number of oxygen atoms present in the EGOs. PTBO4 and PTBO5 were capable of chelating lithium ions, yielding a photovoltaic performance that was 142% of the performance obtained without the polymer layers (3.0 → 5.2%).

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Experimental details; calculation of the binding constant of TEG-Li+ complexes; detailed in situ PEP mechanism, sequential in situ PEP curve obtained from TBO5, followed by bis-EDOT and illustration of the process; reproducibility of the photovoltaic parameters obtained by 5 devices.The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.5b02411.

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