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The most successful active film morphology in organic photovoltaics is the bulk heterojunction (BHJ). The performance of a BHJ arises from a complex interplay of the spatial organization of the segregated donor and acceptor phases and the local order/quality of the respective phases. These critical morphological features develop dynamically during film formation, and it has become common practice to control them by the introduction of processing additives. Here, in situ grazing incidence X-ray diffraction (GIXD) and grazing incidence small angle X-ray scattering (GISAXS) studies of the development of order in BHJ films formed from the donor polymer poly(3-hexylthiophene) and acceptor phenyl-C61-butyric acid methyl ester under the influence of two common additives, 1,8-octanedithiol and 1-chloronaphthalene, are reported. By comparing optical aggregation to crystallization and using GISAXS to determine the number and nature of phases present during drying, two common mechanisms by which the additives increase P3HT crystallinity are identified. Additives accelerate the appearance of pre-crystalline nuclei by controlling solvent quality and allow for extended crystal growth by delaying the onset of PCBM-induced vitrification. The glass transition effects vary system-to-system and may be correlated to the number and composition of phases present during drying. [ABSTRACT FROM AUTHOR]

Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device. [ABSTRACT FROM AUTHOR]

Colloidal-quantum-dot (CQD) optoelectronics offer a compelling combination of solution processing and spectral tunability through quantum size effects. So far, CQD solar cells have relied on the use of organic ligands to passivate the surface of the semiconductor nanoparticles. Although inorganic metal chalcogenide ligands have led to record electronic transport parameters in CQD films, no photovoltaic device has been reported based on such compounds. Here we establish an atomic ligand strategy that makes use of monovalent halide anions to enhance electronic transport and successfully passivate surface defects in PbS CQD films. Both time-resolved infrared spectroscopy and transient device characterization indicate that the scheme leads to a shallower trap state distribution than the best organic ligands. Solar cells fabricated following this strategy show up to 6% solar AM1.5G power-conversion efficiency. The CQD films are deposited at room temperature and under ambient atmosphere, rendering the process amenable to low-cost, roll-by-roll fabrication. [ABSTRACT FROM AUTHOR]