Brett M. Savoie

Unequal Partnership: Asymmetric Roles of Polymeric Donor and Fullerene Acceptor in Generating Free Charge

Natural photosynthetic complexes accomplish the rapid conversion of photoexcitations into spatially separated electrons and holes through precise hierarchical ordering of chromophores and redox centers. In contrast, organic photovoltaic (OPV) cells are poorly ordered, utilize only two different chemical potentials, and the same materials that absorb light must also transport charge; yet, some OPV blends achieve near-perfect quantum efficiency. Here we perform electronic structure calculations on large clusters of functionalized fullerenes of different size and ordering, predicting several features of the charge generation process, outside the framework of conventional theories but clearly observed in ultrafast electro-optical experiments described herein. We show that it is the resonant coupling of photogenerated singlet excitons to a high-energy manifold of fullerene electronic states that enables efficient charge generation, bypassing localized charge-transfer states. In contrast to conventional views, our findings suggest that fullerene cluster size, concentration, and dimensionality control charge generation efficiency, independent of exciton delocalization.

The Next Breakthrough for Organic Photovoltaics

While the intense focus on energy level tuning in organic photovoltaic materials has afforded large gains in device performance, we argue here that strategies based on microstructural/morphological control are at least as promising in any rational design strategy. In this work, a meta-analysis of ∼150 bulk heterojunction devices fabricated with different materials combinations is performed and reveals strong correlations between power conversion efficiency and morphology-dominated properties (short-circuit current, fill factor) and surprisingly weak correlations between efficiency and energy level positioning (open-circuit voltage, enthalpic offset at the interface, optical gap). While energy level positioning should in principle provide the theoretical maximum efficiency, the optimization landscape that must be navigated to reach this maximum is unforgiving. Thus, research aimed at developing understanding-based strategies for more efficient optimization of an active layer microstructure and morphology are likely to be at least as fruitful.

Modeling geminate pair dissociation in organic solar cells: high power conversion efficiencies achieved with moderate optical bandgaps

We propose a model for geminate electron–hole dissociation in organic photovoltaic (OPV) cells and show how power conversion efficiencies greater than those currently achieved might be realized via design strategies employing moderate optical bandgaps and enhanced charge delocalization near the donor–acceptor interface. Applying this model to describing geminate electron–hole dissociation via charge transfer (CT) states, we find good agreement with recently published high-efficiency experimental data. The optimal bandgap for current-generation organic active layer materials is argued to be ∼1.7 eV – significantly greater than in previous analyses, including the Shockley–Queisser approach based upon non-excitonic solar cell dynamics. For future higher efficiency OPVs, the present results show that the optimal bandgap should be slightly lower, ∼1.6 eV. Finally, these results support design strategies aimed at enhancing mobility near the donor–acceptor interface and reducing the electron–hole binding energy, rather than striving to further reduce the bandgap.

Mesoscale molecular network formation in amorphous organic materials

Significance Rapid and robust charge transport in soft matter semiconductors enables technologies such as photovoltaics, transistors, and light-emitting diodes. However, even at a conceptual level it remains unresolved what transport limitations are engendered by the structural disorder typical of soft materials. A graph methodology has been developed to quantify the mesoscopic electrical connectivity of clusters of molecules and its susceptibility to structural disorder. It is observed that some materials exhibit the capacity to regularly form conductive networks that percolate the material volume, even in the absence of periodic order. Moreover, the network properties of electrically percolating materials are qualitatively distinguished from nonpercolating materials, although both are comprised of ostensibly similar molecular units in terms of chemical structure, energy levels, and dimensionality. High-performance solution-processed organic semiconductors maintain macroscopic functionality even in the presence of microscopic disorder. Here we show that the functional robustness of certain organic materials arises from the ability of molecules to create connected mesoscopic electrical networks, even in the absence of periodic order. The hierarchical network structures of two families of important organic photovoltaic acceptors, functionalized fullerenes and perylene diimides, are analyzed using a newly developed graph methodology. The results establish a connection between network robustness and molecular topology, and also demonstrate that solubilizing moieties play a large role in disrupting the molecular networks responsible for charge transport. A clear link is established between the success of mono and bis functionalized fullerene acceptors in organic photovoltaics and their ability to construct mesoscopically connected electrical networks over length scales of 10 nm.

Stokes shift/emission efficiency trade-off in donor–acceptor perylenemonoimides for luminescent solar concentrators

Perylenediimides (PDIs) are among the best performing organic luminescent materials, both in terms of emission efficiency and chemical and photochemical stability because of their rigid, symmetric and planar structure; however, they exhibit very small Stokes shifts. The sizeable reabsorption of the emitted light limits the performances of perylenediimides in imaging applications and luminescent solar concentrators. Perylenemonoimides (PMIs) having an electron donating substituent in one of the free peri positions feature larger Stokes shift values while retaining high chemical stability. The selection of the most appropriate donor, both in terms of electron donating capability and steric demand, boosts emission efficiency and limits reabsorption losses. The synthesis, optical spectroscopy, molecular orbital computations, UPS, electrochemical, spectroelectrochemical, and multinuclear NMR investigation of a series of PMI derivatives functionalized with donors having different electronic characteristics and steric demands are discussed. Results are relevant for the fabrication of single layer plastic luminescent solar concentrators (LSC).

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.

Organic photovoltaics: elucidating the ultra-fast exciton dissociation mechanism in disordered materials.

Organic photovoltaics (OPVs) offer the opportunity for cheap, lightweight and mass-producible devices. However, an incomplete understanding of the charge generation process, in particular the timescale of dynamics and role of exciton diffusion, has slowed further progress in the field. We report a new Kinetic Monte Carlo model for the exciton dissociation mechanism in OPVs that addresses the origin of ultra-fast (<1 ps) dissociation by incorporating exciton delocalization. The model reproduces experimental results, such as the diminished rapid dissociation with increasing domain size, and also lends insight into the interplay between mixed domains, domain geometry, and exciton delocalization. Additionally, the model addresses the recent dispute on the origin of ultra-fast exciton dissociation by comparing the effects of exciton delocalization and impure domains on the photo-dynamics.This model provides insight into exciton dynamics that can advance our understanding of OPV structure-function relationships.

A Simple Index for Characterizing Charge Transport in Molecular Materials

While advances in quantum chemistry have rendered the accurate prediction of band alignment relatively straightforward, the ability to forecast a noncrystalline, multimolecule systems conductivity possesses no simple computational form. Adapting the theory of classical resistor networks, we develop an index for quantifying charge transport in bulk molecular materials, without the requirement of crystallinity. The basic behavior of this index is illustrated through its application to simple lattices and clusters of common organic photovoltaic molecules, where it is shown to reproduce experimentally known performances for these materials. This development provides a quantitative computational means for determining a priori the bulk charge transport properties of molecular materials.

Systematic evaluation of structure–property relationships in heteroacene – diketopyrrolopyrrole molecular donors for organic solar cells

Improved understanding of fundamental structure–property relationships, particularly the effects of molecular shape and intermolecular packing on film morphology and active layer charge transport characteristics, enables more rational synthesis of new p-type small molecules. Here we investigate a series of small molecules consisting of an acene-based electron-rich core flanked by one or two electron-deficient diketopyrrolopyrrole (DPP) moieties. Through minor changes in the molecule structures, measurable variations in the crystal structure and sizable differences in macroscopic properties are achieved. The molecular symmetry as well as the conformation of the side chains affects the unit cell packing density and strength of the intermolecular electronic coupling in single crystals of all molecules in this series. The addition of a second DPP unit to the benzodithiophene (BDT) core increases molecular planarity leading to decreased reorganization energy, strong cofacial coupling, and moderate hole mobility (2.7 × 10−4 cm2 V−1 s−1). Increasing the length of the acene core from benzodithiophene to naphthodithiophene (NDT) results in a further reduction in reorganization energy and formation of smaller crystalline domains (∼11 nm) when mixed with PCBM. Decreasing the aspect ratio of the core using a “zig-zag” naphthodithiophene (zNDT) isomer results in the highest hole mobility of 1.3 × 10−3 cm2 V−1 s−1 due in part to tight lamellar (d = 13.5 A) and π–π stacking (d = 3.9 A). The hole mobility is directly correlated with the short-circuit current (11.7 mA cm−2) and solar cell efficiency (4.4%) of the highest performing zNDT:PCBM device. For each of these small molecules the calculated π-coupling constant is correlated with the hole mobility as a function of crystal structure and orientation indicating the importance of designing molecules that create extended crystalline networks with maximal π-orbital overlap.

Elimination of Butylcycloheptylprodigiosin as a Known Natural Product Inspired by an Evolutionary Hypothesis for Cyclic Prodigiosin Biosynthesis

The cyclic prodigiosins are an important family of bioactive natural products that continue to be the subject of numerous structural, synthetic, and biosynthetic studies. In particular, the structural assignments of the isomeric cyclic prodigiosins butylcycloheptylprodigiosin (BCHP) and streptorubin B have been the cause of significant confusion. Herein, we report detailed studies regarding the electron impact (EI) mass spectra of synthetic BCHP and streptorubin B that have allowed us to distinguish the two compounds in the absence of quality historical isolation NMR data. On the basis of these fragmentation differences, the status of BCHP as a natural product is challenged. The proposed mechanism of fragmentation is supported by the EI mass spectra of synthetic pentyl-chain analogues of BCHP and streptorubin B, X-ray crystallography, and DFT calculations. Elimination of BCHP from the prodigiosin family supports a proposed evolutionary hypothesis for the surprising biosynthesis of cyclic prodigiosins.