Low-temperature solution-processed thiophene-sulfur-doped planar ZnO nanorods as electron-transporting layers for enhanced performance of organic solar cells

1-D ZnO represents a fascinating class of nanostructures that are significant to optoelectronics. In this work, we investigated the use of an eco-friendly, metal free in situ doping through a pure thiophene-sulfur (S) on low temperature processed (<95 °C) and annealed (<170 °C), planar 1-D ZnO nanorods (ZnRs) spin-coated as a holeblocking and electron transporting layer (ETL) for inverted organic solar cells (iOSCs). The TEM, HRTEM, XPS, FT-IR, EDS and Raman studies clearly reveal that the thiophene-S (Thi-S) atom is incorporated on planar ZnRs. The investigations in electrical properties suggest the enhancement in conductivity after Thi-S doping on 1-D ZnRs. The iOSCs of poly(3-hexylthiophene-2,5-diyl) and phenyl-C₆₁-butyric acid methyl ester (P3HT: PC₆₀BM) photoactive layer containing thiophene-S doped planar ZnRs (Thi-S-PZnRs) as ETL exhibits power conversion efficiency (PCE) of 3.68% under simulated AM 1.5 G, 100 mW cm^-2 illumination. The ∼47% enhancement in PCE compared with pristine planar ZnRs (PCE = 2.38%) ETL is attributed to a combination of desirable energy level alignment, morphological modification, increased conductivity and doping effect. The universality of Thi-S-PZnRs ETL is demonstrated by the highest PCE of 8.15% in contrast to 6.50% exhibited by the iOSCs of ZnRs ETL for the photoactive layer comprising of poly[4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)benzo[1,2-b;4,5-b]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]: phenyl-C71-butyric acid methyl ester (PTB7-Th: PCB₇₁M). This enhancement in PCE is observed to be driven mainly through improved photovoltaic parameters like fill factor (ff) as well as photocurrent density (J_sc), which are assigned to increased conductivity, exciton dissociation, and effective charge extraction, while; better ohmic contact, reduced charge recombination, and low leakage current density resulted in increased V_oc.