A series of small compound materials based on benzodithiophene (BDT) and diketopyrrolopyrrole (DPP) with three different alkyl side chains were synthesized and used for organic photovoltaics. These small compounds had different alkyl branches (i.e., 2-ethylhexyl (EH), 2-butyloctyl (BO), and 2-hexyldecyl (HD)) attached to DPP units. Thin films made of these compounds were characterized and their solar cell parameters were measured in order to systematically analyze influences of the different side chains of compounds on the film microstructure, molecular packing, and hence, charge-transport and recombination properties. The relatively shorter side chains in the small molecules enabled more ordered packing structures with higher crystallinities, which resulted in higher carrier mobilities and less recombination factors; the small molecule with the EH branches exhibited the best semiconducting properties with a power conversion efficiency of up to 5.54% in solar cell devices. Our study suggested that tuning the alkyl chain length of semiconducting molecules is a powerful strategy for achieving high performance of organic photovoltaics.

In bulk heterojunction (BHJ) organic photovoltaics, particularly those using small molecules, electron donor and/or electron acceptor materials form a distributed network in the photoactive layer where critical photo-physical processes occur. Extensive research has recently focused on the importance of sulfur atoms in the small molecules. Little is known about the three-dimensional orientation of these sulfur atom-containing molecules. Herein, we report on our research concerning the heterojunction textures of the crystalline molecular orientation of small compounds having sulfur-containing units in the side chains, specifically, compounds known as DR3TSBDT that contain the alkylthio group and DR3TBDTT that does not. The improved performance of the DR3TBDTT-based devices, particularly in the photocurrent and the fill factor, was attributed to the large population of donor compound crystallites with a favorable face-on orientation along the perpendicular direction. This orientation resulted in efficient charge transport and a reduction in charge recombination. These findings underscore the great potential of small-molecule solar cells and suggest that even higher efficiencies can be achieved through materials development and molecular orientation control.

We report a comparison of charge carrier kinetics and recombination dynamics correlated with the device performances of PBDTTT-C and PBDTTT-CT in nonfullerene P­(NDI2OD-T2) solar cells. The nanoscale morphological characteristics are found to be remarkably different for these two polymers in all-polymer bulk heterojunction (BHJ) blends. Important insights into the carrier dynamics and crystalline packing features of these different donor materials are provided in detail. The higher device performance of the PBDTTT-CT:P­(NDI2OD-T2) device [2.78% compared to 1.56% for the PBDTTT-C:P­(NDI2OD-T2) cell] is shown to result from efficient charge generation and faster carrier separation, reducing nongeminate recombination during charge collection, which is attributed to the perfect intermixing between the donor and acceptor polymer networks.

All-polymer solar cells are herein presented utilizing the PBDTTT-CT donor and the P(NDI2OD-T2) acceptor with 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) binary solvent additives. A systematic study of the polymer/polymer bulk heterojunction photovoltaic cells processed from the binary additives revealed that the microstructures and photophysics were quite different from those of a pristine system. The combination of DIO and CN with a DIO/CN ratio of 3:1 (3 vol% DIO, 1 vol% CN and 96 vol% o-DCB) led to suitable penetrating polymer networks, efficient charge generation and balanced charge transport, which were all beneficial to improving the efficiency. This improvement is attributed to increase in power conversion efficiency from 2.81% for a device without additives to 4.39% for a device with the binary processing additives. A detailed investigation indicates that the changes in the polymer:polymer interactions resulted in the formation of a percolating nasnoscale morphology upon processing with the binary additives. Depth profile measurements with a two-dimensional grazing incidence wide-angle X-ray scattering confirm this optimum phase feature. Furthermore impedance spectroscopy also finds evidence for synergistically boosting the device performance.

A key challenge to the commercialization of solution-processed solar cells is a proper understanding of the morphological variations during long periods, particularly under light-soaking conditions. Many research groups have competitively reported solvent vapor annealing (SVA)-treated small-molecule devices with efficiency rates exceeding 11%; however, their light-soaking effects have been rarely studied. Here, we investigate the morphological changes in the light-soaked devices with/without SVA treatments depending on the illumination time via three-dimensional observations. From the results, we found that the trends of morphological variations differ in the surface and bulk parts of the active film and that the difference is closely related to the device performance capabilities. Therefore, our research will enhance the underlying knowledge of the light-soaking effect on active morphologies over long term.