An inorganic p‐type CuInS2 semiconductor was combined with the semiconducting polymer of PNDI3OT‐Se1 and PNDI3OT‐Se2 with different HOMO/LUMO levels for photoelectrochemical hydrogen production. Charge transfer behaviors at polymer/CuInS2 junctions were investigated by electrochemical impedance spectroscopy. The heterojunction of p‐CuInS2 and n‐type polymer (both PNDI3OT‐Se1 and Se2) successfully made p‐n junctions and showed improved charge transfer. However, we found that higher HOMO levels of polymer than valence band maximum (VBM) of CuInS2 spurred charge recombination at interfaces. As a result, CuInS2/PNDI3OT‐Se1/TiO2/Pt, which has suitable energy levels matched between PNDI3OT‐Se1 and CuInS2, shows photocurrent (−15.67 mA cm−2) improved concretely when compared to a CuInS2/TiO2/Pt photoelectrode (−7.11 mA cm−2) at 0.0 V vs. RHE applied potential. Additionally, the photoelectrochemical stability of CuInS2/PNDI3OT‐Se1/TiO2/Pt photoelectrode was also investigated.

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Organic solar cells (OSCs) demonstrating high power conversion efficiencies have been mostly fabricated using halogenated solvents, which are highly toxic and harmful to humans and the environment. Recently, non-halogenated solvents have emerged as a potential alternative. However, there has been limited success in attaining an optimal morphology when non-halogenated solvents (typically o-xylene (XY)) were used. To address this issue, we studied the dependence of the photovoltaic properties of all-polymer solar cells (APSCs) on various high-boiling-point non-halogenated additives. We synthesized PTB7-Th and PNDI2HD-T polymers that are soluble in XY and fabricated PTB7-Th:PNDI2HD-T-based APSCs using XY with five additives: 1,2,4-trimethylbenzene (TMB), indane (IN), tetralin (TN), diphenyl ether (DPE), and dibenzyl ether (DBE). The photovoltaic performance was determined in the following order: XY + IN < XY + TMB < XY + DBE ≤ XY only < XY + DPE < XY + TN. Interestingly, all APSCs processed with an XY solvent system had better photovoltaic properties than APSCs processed with chloroform solution containing 1,8-diiodooctane (CF + DIO). The key reasons for these differences were unraveled using transient photovoltage and two-dimensional grazing incidence X-ray diffraction experiments. The charge lifetimes of APSCs based on XY + TN and XY + DPE were the longest, and their long lifetime was strongly associated with the polymer blend film morphology; the polymer domain sizes were in the nanoscale range, and the blend film surfaces were smoother, as the PTB7-Th polymer domains assumed an untangled, evenly distributed, and internetworked morphology. Our results demonstrate that the use of an additive with an optimal boiling point facilitates the development of polymer blends with a favorable morphology and can contribute to the widespread use of eco-friendly APSCs.