In this study, we employed polyethylenimine-doped sol-gel-processed zinc oxide composites (ZnO:PEI) as efficient electron transport layers (ETL) for facilitating electron extraction in inverted polymer solar cells. Using ultraviolet photoelectron spectroscopy, synchrotron grazing-incidence small-angle X-ray scattering and transmission electron microscopy, we observed that ZnO:PEI composite films' energy bands could be tuned considerably by varying the content of PEI up to 7 wt %-the conduction band ranged from 4.32 to 4.0 eV-and the structural order of ZnO in the ZnO:PEI thin films would be enhanced to align perpendicular to the ITO electrode, particularly at 7 wt % PEI, facilitating electron transport vertically. We then prepared two types of bulk heterojunction systems-based on poly(3-hexylthiophene) (P3HT):phenyl-C61-butryric acid methyl ester (PC61BM) and benzo[1,2-b:4,5-b́]dithiophene-thiophene-2,1,3-benzooxadiazole (PBDTTBO):phenyl-C71-butryric acid methyl ester (PC71BM)-that incorporated the ZnO:PEI composite layers. When using a composite of ZnO:PEI (93:7, w/w) as the ETL, the power conversion efficiency (PCE) of the P3HT:PC61BM (1:1, w/w) device improved to 4.6% from a value of 3.7% for the corresponding device that incorporated pristine ZnO as the ETL-a relative increase of 24%. For the PBDTTBO:PC71BM (1:2, w/w) device featuring the same amount of PEI blended in the ETL, the PCE improved to 8.7% from a value of 7.3% for the corresponding device that featured pure ZnO as its ETL-a relative increase of 20%. Accordingly, ZnO:PEI composites can be effective ETLs within organic photovoltaics.

Conjugated polymer/nanocrystal composites have attracted much attention for use in renewable energy applications because of their versatile and synergistic optical and electronic properties. Upon absorbing photons, charge separation occurs in the nanocrystals, generating electrons and holes for photocurrent flow or reduction/oxidation (redox) reactions under proper conditions. Incorporating these nanocrystals into conjugated polymers can complement the visible light absorption range of the polymers for photovoltaics applications or allow the polymers to sensitize or immobilize the nanocrystals for photocatalysis. Here, the current developments of conjugated polymer/nanocrystal nanocomposites for bulk heterojunction-type photovoltaics incorporating Cd- and Pb-based nanocrystals or quantum dots are reviewed. The effects of manipulating the organic ligands and the concentration of the nanocrystal precursor, critical factors that affect the shape and aggregation of the nanocrystals, are also discussed. In the conclusion, the mechanisms through which conjugated polymers can sensitize semiconductor nanocrystals (TiO2 , ZnO) to ensure efficient charge separation, as well as how they can support immobilized nanocrystals for use in photocatalysis, are addressed.

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We discuss the packing characteristics and photovoltaic device performance of the donor–acceptor conjugated polymers with 1-D, branched and 2-D molecular architectures.