Jessica E. Coughlin

Design and Synthesis of Molecular Donors for Solution-Processed High-Efficiency Organic Solar Cells

Organic semiconductors incorporated into solar cells using a bulk heterojunction (BHJ) construction show promise as a cleaner answer to increasing energy needs throughout the world. Organic solar cells based on the BHJ architecture have steadily increased in their device performance over the past two decades, with power conversion efficiencies reaching 10%. Much of this success has come with conjugated polymer/fullerene combinations, where optimized polymer design strategies, synthetic protocols, device fabrication procedures, and characterization methods have provided significant advancements in the technology. More recently, chemists have been paying particular attention to well-defined molecular donor systems due to their ease of functionalization, amenability to standard organic purification and characterization methods, and reduced batch-to-batch variability compared to polymer counterparts. There are several critical properties for efficient small molecule donors. First, broad optical absorption needs to extend towards the near-IR region to achieve spectral overlap with the solar spectrum. Second, the low lying highest occupied molecular orbital (HOMO) energy levels need to be between -5.2 and -5.5 eV to ensure acceptable device open circuit voltages. Third, the structures need to be relatively planar to ensure close intermolecular contacts and high charge carrier mobilities. And last, the small molecule donors need to be sufficiently soluble in organic solvents (≥10 mg/mL) to facilitate solution deposition of thin films of appropriate uniformity and thickness. Ideally, these molecules should be constructed from cost-effective, sustainable building blocks using established, high yielding reactions in as few steps as possible. The structures should also be easy to functionalize to maximize tunability for desired properties. In this Account, we present a chronological description of our thought process and design strategies used in the development of highly efficient molecular donors that achieve power conversion efficiencies greater than 7%. The molecules are based on a modular D(1)-A-D(2)-A-D(1) architecture, where A is an asymmetric electron deficient heterocycle, which allowed us to quickly access a library of compounds and develop structure-property-performance relationships. Modifications to the D1 and D2 units enable spectral coverage throughout the entire visible region and control of HOMO energy levels, while adjustments to the pendant alkyl substituents dictate molecular solubility, thermal transition temperatures, and solid-state organizational tendencies. Additionally, we discuss regiochemical considerations that highlight how individual atom placements can significantly influence molecular and subsequently device characteristics. Our results demonstrate the utility of this architecture for generating promising materials to be integrated into organic photovoltaic devices, call attention to areas for improvement, and provide guiding principles to sustain the steady increases necessary to move this technology forward.

All-Organic and Fully-Printed Semitransparent Photodetectors Based on Narrow Bandgap Conjugated Molecules

All-organic, fully-printed and semitransparent photodetectors with a broad wavelength band response, based on a ternary blend comprising narrow band-gap small molecules, are demonstrated. The ternary blend with a semiconducting polymer allows for the optimal printing of small molecules, suppressing strong phase segregation, and uncontrolled crystallization. The insertion of a suitable interlayer enables the adoption of polymer, transparent, top and bottom printed electrodes, thus making light detection possible from both device sides.

Topological Considerations for the Design of Molecular Donors with Multiple Absorbing Units

The molecule AT1, with two weakly conjugated chromophores, was designed, synthesized, and examined within the context of its film forming tendencies. While the addition of the second chromophore to the central core enables broadening of the absorption spectrum, this change is mostly apparent in films that are grown slowly. Grazing incidence X-ray scattering (GIWAXS) analysis indicates that these spectral characteristics correspond to an increase in solid state ordering. This information, in combination with differential scanning calorimetry, suggests that the overall molecular shape provides a kinetic barrier to crystallization. As a result, one finds the absence of molecular order when AT1 is combined with PC71BM in solution-cast blends. These findings highlight the importance of molecular topology when designing molecular components for solar cell devices.

Polymorphism of Crystalline Molecular Donors for Solution-Processed Organic Photovoltaics

Using ab initio calculations and classical molecular dynamics simulations coupled to complementary experimental characterization, four molecular semiconductors were investigated in vacuum, solution, and crystalline form. Independently, the molecules can be described as nearly isostructural, yet in crystalline form, two distinct crystal systems are observed with characteristic molecular geometries. The minor structural variations provide a platform to investigate the subtlety of simple substitutions, with particular focus on polymorphism and rotational isomerism. Resolved crystal structures offer an exact description of intermolecular ordering in the solid state. This enables evaluation of molecular binding energy in various crystallographic configurations to fully rationalize observed crystal packing on a basis of first-principle calculations of intermolecular interactions.

Molecular orientation within thin films of isomorphic molecular semiconductors

Four isomorphic organic semiconductors are compared to map out how the precision of chemical structures determines solid state molecular organization. Intramolecular electronic structure and intermolecular packing preference in the solid state were shown to be exclusively dependent on the relative location of the electron accepting fragments within a given molecule.

Efficient solution-processed small-molecule solar cells with titanium suboxide as an electric adhesive layer

We demonstrate efficient and air-stable small-molecule bulk heterojunction (SM BHJ) solar cells by introducing titanium suboxide (TiOx) between the active layer and the cathode as an electric adhesive layer. The SM BHJ solar cell with the TiOx interlayer exhibits improved power conversion efficiency of 6.4% as well as greatly enhanced device lifetime. Analysis of the dark diode characteristics and comparison of the current density-voltage characteristics upon heat annealing indicate that the TiOx interlayer improves the electrical contact between the active layer and the cathode, thereby resulting in efficient sweep-out of photogenerated charge carriers.