Jojo A. Amonoo

Recovering lost excitons in organic photovoltaics using a transparent dissociation layer

In organic photovoltaic (OPV) cells, photocurrent generation relies on exciton diffusion to the donor/acceptor heterojunction. Excitons that fail to reach the heterojunction are lost to recombination via quenching at the electrodes or relaxation in the bulk. Bulk recombination has been mitigated largely through the use of bulk heterojunctions, while quenching at the metal cathode has been previously circumvented through the introduction of exciton blocking layers that “reflect” excitons. Here, we investigate an alternative concept of a transparent exciton dissociation layer (EDL), a single layer that prevents exciton quenching at the electrode while also providing an additional interface for exciton dissociation. The additional heterojunction reduces the distance excitons must travel to dissociate, recovering the electricity-generating potential of excitons otherwise lost to heat. We model and experimentally demonstrate this concept in an archetypal subphthalocyanine/fullerene planar heterojunction OPV, generating an extra 66% of photocurrent in the donor layer (resulting in a 27% increase in short-circuit current density from 3.94 to 4.90 mA/cm2). Because the EDL relaxes the trade-off between exciton diffusion and optical absorption efficiencies in the active layers, it has broad implications for the design of OPV architectures and offers additional benefits over the previously demonstrated exciton blocking layer for photocurrent generation.

An all-conjugated gradient copolymer approach for morphological control of polymer solar cells

This work introduces fully π-conjugated gradient copolymers as promising materials to control and stabilize the nanoscale morphology of polymer:fullerene solar cells. Gradient and block sequence copolymers of 3-hexylselenophene (3HS) and 3-hexylthiophene (3HT) are utilized as the donors (D) in bulk-heterojunction (BHJ) solar cells with phenyl-C61-butyric acid methyl ester (PCBM) as the acceptor (A). We show that for the same overall copolymer composition, the ordering of molecular constituents along the copolymer chain (copolymer sequence) significantly influences the nanoscale morphology and phase separation behavior of π-conjugated copolymer:fullerene devices. In addition, energy-filtered transmission electron microscopy (EFTEM) of the blends revealed that relative to the block copolymer:PCBM, the gradient copolymer:PCBM sample formed a more uniform, continuous and interconnected network of polymer fibrils within the acceptor-rich phase, associated with a large D/A interface. Charge extraction of photogenerated carriers by linearly increasing voltage (photo-CELIV) shows that the gradient copolymer:PCBM device possesses the highest initial carrier density, n(0) = (3.92 ± 0.3) × 1018 cm−3, consistent with a larger D/A interfacial area suggested by the observed morphology, albeit at the expense of increased carrier recombination rate. Accelerated degradation studies show that the gradient copolymer:PCBM system maintains the highest efficiency over prolonged heat treatment.

Reduction of open circuit voltage loss in a polymer photovoltaic cell via interfacial molecular design: Insertion of a molecular spacer

Loss to the open circuit voltage (Voc) in organic photovoltaic cells is a critical bottleneck to achieving high power conversion efficiency. We demonstrate that the insertion of multilayers of a poly(phenylene ethynylene) spacer into the planar heterojunction between poly(3-hexylthiophene) and phenyl-C61-butyric acid methyl ester incrementally escalates the Voc of a polymer solar cell from 0.43 V to 0.9 V. Through a combination of light intensity and temperature dependent measurements, we show that this control over the molecular structure local to the interface increases Voc by raising the polaron pair energy and by suppressing the dark-diode current.

Surprisingly High Conductivity and Efficient Exciton Blocking in Fullerene/Wide-Energy-Gap Small Molecule Mixtures

We find that mixtures of C60 with the wide energy gap, small molecular weight semiconductor bathophenanthroline (BPhen) exhibit a combination of surprisingly high electron conductivity and efficient exciton blocking when employed as buffer layers in organic photovoltaic cells. Photoluminescence quenching measurements show that a 1:1 BPhen/C60 mixed layer has an exciton blocking efficiency of 84 ± 5% compared to that of 100% for a neat BPhen layer. This high blocking efficiency is accompanied by a 100-fold increase in electron conductivity compared with neat BPhen. Transient photocurrent measurements show that charge transport through a neat BPhen buffer is dispersive, in contrast to nondispersive transport in the compound buffer. Interestingly, although the conductivity is high, there is no clearly defined insulating-to-conducting phase transition with increased insulating BPhen fraction. Thus, we infer that C60 undergoes nanoscale (<10 nm domain size) phase segregation even at very high (>80%) BPhen fractions.