Squaraines offer significant potential for organic photovoltaics because of their broad absorbance and high extinction coefficients as well as their expected use as mechanistic probes in such devices. In this work steps are taken to develop a comprehensive understanding of the excited state properties of squaraines, based on their molecular structure and the resulting solid state packing. Accurate assignments of the absorption spectral peaks are made based on an essential states model, expanded to include intermolecular charge transfer (ICT). Comparison of simulated spectra with spectra for two symmetric squaraine derivatives confirms that ICT has a major influence on the optical and electronic properties of squaraine aggregates, fully accounting for the origin of the strong panchromaticity of these systems.

Aggregates of quadrupolar DAD-type chromophores are investigated theoretically using the essential states model (ESM) enhanced to include vibronic coupling. On the basis of vibronic signatures in the absorption and photoluminescence spectra, important connections are made to the Frenkel exciton model, which is the basis for defining conventional H-and J-aggregates. In contrast to the exciton theory, the ESM allows for an unusual type of the red-shif ted Haggregate, driven by the large quadrupole−quadrupole interaction. Except for the red shift of the main absorption peak, such aggregates display all of the characteristics of conventional Haggregates, including suppressed radiative decay rates and all of the vibronic signatures in the absorption and photoluminescence spectra consistent with Frenkel exciton models. Red-shifted Hdimers occur for a range of slip angles, which separate conventional H-and J-aggregate behavior, with the slip range diminishing with increasing intermolecular separation. Davydov splitting and vibronic signatures for dimers with nonparallel transition dipole moments are also investigated. The theoretical insight provided herein may be exploited for optimizing optoelectronic device applications for growing families of quadrupolar molecules.

a b s t r a c tSmall conjugated molecules are of great interest as promising alternatives to semiconducting polymers in organic photovoltaics (OPV). In this work, we introduce a more accurate assignment of the excited state of a promising squaraine (SQ) targeted for OPV application. From this assignment, we conclude that a mixed population of monomers and aggregates exists in spin-cast SQ:PC 61 BM bulk heterojunction (BHJ) films, where monomers indicate the presence of amorphous regions that could act as traps. Since crystallinity is critically important for efficient charge transport and exciton diffusion in the BHJ, we thermally anneal the as-cast films to reduce the amorphous regions. Our analysis of annealed films demonstrates a delicate trade-off between increased crystallinity and larger domain sizes. Crystallinity improves but often at the expense of larger crystal size, as supported by XRD and TEM study. Therefore, to achieve optimal OPV efficiency, we controlled the tradeoff to improve the crystallinity while maintaining a small, highly mixed BHJ morphology. We thus highlight the importance of chemical compatibility when designing small molecules for use in high efficiency BHJ devices. Significantly, we have connected theoretically validated spectroscopic assignment with the first full study of morphology and domain size control as they affect small molecule OPV active layers.

In this work, we have investigated a series of aniline-based squaraines, with varying solubilizing alkyl chains, as donor materials in bulk heterojunction (BHJ) solar cells. Although these squaraine molecules exhibit similar absorbance spectra and crystal structures, the difference in properties that drive the OPV performance becomes apparent when each squaraine is blended with PCBM. Thin film X-ray diffraction results demonstrate a disruption of squaraine crystallization in the presence of PCBM, more so for shorter side chain squaraines. As a result, the hole mobilities of BHJ films of shorter side chain squaraines show the largest drop when compared to their neat films, whereas the mobility decrease for the longer side chain counterparts is small. However, morphological studies have shown that the phase separation rapidly happens during the spin-casting process for longer side chain squaraines. Ultimately, it is the extent of phase separation that dominates the final device efficiency. Therefore, rational design can greatly be influenced as a result of our systematic materials properties overview for anilinic squaraines targeted for OPV.

Squaraine dyes have significant potential for use in organic photovoltaic devices because their chemical and packing structure tunability leads to a broad solid state panchromaticity. Nevertheless, broadening of the spectrum does not always give rise to increasing power conversion efficiencies. Furthermore, the same processing strategy used to make devices from different squaraines does not lead to the same optimized performance. In this work, by varying the environmental conditions of a set of anilinic squaraines, we demonstrate that spin-cast thin films are made up of a complex set of states, with each state contributing differently to the overall device efficiency. We demonstrate crystallochromy in that small changes in the packing structure give rise to dramatically different absorption spectra. Through a remarkable comparison between squaraines in poly(methyl methacrylate) solid solution and squaraine:PC60BM blends, we also show long-range and orientational disorder broadening, which distorts the ability to correlate qualitative spectroscopic assessment with an understanding of the device mechanism. We conclude that a full quantitative assessment of the populations of each excited state must be carried out in order to make progress toward an improved understanding of each state's contribution to charge transfer at the bulk heterojunction interface.