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In Situ GIWAXS Analysis of Solvent and Additive Effects on PTB7 Thin Film Microstructure Evolution during Spin
Eric F Manley1,2, Joseph Strzalka3, Thomas J Fauvell1,2
1Department of Chemistry and the Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA.
Abstract:
The influence of solvent and processing additives on the pathways and rates of crystalline morphology formation for spin-coated semiconducting PTB7 (poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)-carbonyl]-thieno[3,4-b]thiophenediyl]]) thin films is investigated by in situ grazing incidence wide-angle X-ray scattering (GIWAXS) and optical reflectance, to better understand polymer solar cell (PSC) optimization approaches. In situ characterization of PTB7 film formation from chloroform (CF), chlorobenzene (CB), and 1,2-dichlorobenzene (DCB) solutions, as well as CB solutions with 1% and 3% v/v of the processing additives 1-chloronapthalene (CN), diphenylether (DPE), and 1,8-diiodooctane (DIO), reveals multiple crystallization pathways with: (i) single-solvent systems exhibiting rapid (<3 s) crystallization after a solvent boiling point-dependent film thinning transition, (ii) solvent + additive systems exhibiting different crystallization pathways and crystallite formation times from minutes (CN, DPE) to 1.5 h (DIO). Identifying crystalline intermediates has implications for bulk-heterojunction PSC morphology optimization via optimized spin-casting processes.
