Stable solvent for solution-based electrical doping…

… of semiconducting polymer films and its application to organic solar cells.

Controlled and stable electrical doping of organic semiconductors is desirable for the realization of efficient organic photovoltaic (OPV) devices. Thus, progress has been made to understand the fundamental doping mechanisms.1-3 In 2016, Aizawa et al. reported the use of 12-molybdophosphoric acid hydrate (PMA) to induce p-type doping and crosslinking of neat films of poly[N-9’-heptadecanyl-2,7-carbazole-alt-5,5-(4’,7’-di-2-thienyl-2’,1’,3’-benzothiadiazole)](PCDTBT).4 Later on, a more general approach of sequential solution-based doping was presented, by post-process immersion of donor-like polymer films in PMA-nitromethane solutions.5 However, critical to the method is the use of nitromethane, a highly unstable solvent, to dissolve PMA and thus limited the applicability to large-scale fabrication of organic solar cells.

A collaboration between a team of researchers from the Kippelen Research Group at Georgia Tech and the Toney Research Group at SSRL developed a solution-based doping method using the highly stable solvent, acetonitrile. Figure 1a displays the chemicals used in this work. In Figure 1b, the optical properties of poly(3-hexylthiophene-2,5-diyl)(P3HT) films immersed for 30 min in a 0.5 M solution of PMA in acetonitrile (PMA-im-P3HT) were studied by comparing their transmittance spectra against pristine P3HT and P3HT immersed similarly in a 0.5 M solution of PMA in nitromethane. The normalized change of transmittance ΔT T-1 as a function of wavelength (inset of Fig.1b) reveals the same spectral signatures reported for PMA-im-P3HT films when PMA was dissolved in nitromethane. That is, changes in the region where ΔT T-1< 0 correlate with the P3HT polaron bands, and deviations in the region where ΔT T-1> 0 correlate to the bleaching of the main π-π* absorption bands.6 The data suggests electrical p-doping into the depth of the organic film. Figure 1c shows that the performance of PMA-doped OPV devices using PMA in acetonitrile is comparable to that of OPVs made using PMA in nitromethane or MoO3, under simulated AM 1.5G solar illumination. Furthermore, if the light soaking mechanism is used before each measurement, OPVs made using PMA in nitromethane or acetonitrile remain stable for up to 524 h in the air, retaining 80% of their initial power conversion efficiency (PCE).

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Figure: (extract) of GIWAXS data as measured on pristine and PMA doped P3HT, when using various solvents to dissolve the PMA. a, Two-dimensional GIWAXS data converted to q-space for pristine P3HT and P3HT immersed in PMA solutions in nitromethane, acetonitrile or ethanol for 60 seconds. b, One-dimensional scattering profiles (out-of-plane and in-plane profiles), obtained from the two-dimensional GIWAXS data.