Joseph K. Gallaher

Performance, morphology and photophysics of high open-circuit voltage, low band gap all-polymer solar cells

The microstructure and photophysics of low-band gap, all-polymer photovoltaic blends are presented. Blends are based on the donor polymer BFS4 (a dithienyl-benzo[1,2-b:4,5-b]dithiophene/5-fluoro-2,1,3-benzothiadiazole co-polymer) paired with the naphthalene diimide-based acceptor polymer P(NDI2OD-T2). Efficiencies of over 4% are demonstrated, with an open circuit voltage of greater than 0.9 V achieved. Transmission electron microscopy reveals a relatively coarse phase-separated morphology, with elongated domains up to 200 nm in width. Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy and atomic force microscopy (AFM) measurements reveal that the top surface of BFS4:P(NDI2OD-T2) blends is covered with a pure BFS4 capping layer. Depth profiling measurements confirm this vertical phase separation with a surface-directed spinodal decomposition wave observed. Grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements confirm that BFS4 and P(NDI2OD-T2) are semicrystalline with both polymers retaining their semicrystalline nature when blended. Photoluminescence spectroscopy reveals incomplete photoluminescence quenching with as much as 30% of excitons failing to reach a donor/acceptor interface. Transient absorption spectroscopy measurements also find evidence for rapid geminate recombination.

Thermodynamic Factors Impacting the Peptide-Driven Self-Assembly of Perylene Diimide Nanofibers

Synthetic peptides offer enormous potential to encode the assembly of molecular electronic components, provided that the complex range of interactions is distilled into simple design rules. Here, we report a spectroscopic investigation of aggregation in an extensive series of peptide-perylene diiimide conjugates designed to interrogate the effect of structural variations. By fitting different contributions to temperature dependent optical absorption spectra, we quantify both the thermodynamics and the nature of aggregation for peptides by incrementally varying hydrophobicity, charge density, length, as well as asymmetric substitution with a hexyl chain, and stereocenter inversion. We find that coarse effects like hydrophobicity and hexyl substitution have the greatest impact on aggregation thermodynamics, which are separated into enthalpic and entropic contributions. Moreover, significant peptide packing effects are resolved via stereocenter inversion studies, particularly when examining the nature of aggregates formed and the coupling between π electronic orbitals. Our results develop a quantitative framework for establishing structure-function relationships that will underpin the design of self-assembling peptide electronic materials.

Transient Grating Photoluminescence Spectroscopy: An Ultrafast Method of Gating Broadband Spectra.

Ultrafast photoluminescence (PL) spectroscopy can cleanly resolve excited-state dynamics and coupling to the environment, however, there is a demand for new methods that combine broadband detection and low backgrounds. We present a new method, transient grating photoluminescence spectroscopy (TGPLS), that addresses this challenge by exploiting a focusing geometry where ultrafast broadband spectra are transiently diffracted away from the background PL. We show that TGPLS can resolve the complex spectral relaxation observed in conjugated polymer and oligomer solutions, with an essentially flat spectral response throughout the visible region and potentially beyond. The benefits we demonstrate using TGPLS could expand access to spectral information, particularly for other multichromophoric and heterogeneous materials where complex spectral relaxation is expected.

Spectroscopically tracking charge separation in polymer : fullerene blends with a three-phase morphology

The coexistence of intermixed amorphous polymer : fullerene phases alongside pure semicrystalline polymer and fullerene phases provides a plausible explanation for effective charge separation in organic photovoltaic blends by providing a cascaded energy landscape. We sought to test this proposal by spectroscopically tracking charge dynamics in 3-phase blends compared with binary counterparts and linking these dynamics to free charge yields. Our study applies broadband transient absorption spectroscopy to a series of closely related alternating thiophene–benzothiadiazole copolymers in which the tuned curvature of the polymer backbone controls the nature and degree of polymer–fullerene intermixing. Free charge generation is most efficient in the 3-phase morphology that features intimately mixed polymer : PCBM regions amongst neat polymer and PCBM phases. TA spectral dynamics and polarization anisotropy measurements reveal the sub-nanosecond migration of holes from intermixed to pure polymer regions of such blends. In contrast, 2-phase blends lack the spectral dynamics of this charge migration process and suffer from severe geminate recombination losses. These results provide valuable spectroscopic evidence for an efficient charge separation pathway that relies on the 3-phase morphology.

Endothermic singlet fission is hindered by excimer formation

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

Evolution of Nonmirror Image Fluorescence Spectra in Conjugated Polymers and Oligomers

The nonmirror image relationship between absorption and fluorescence spectra of conjugated polymers contrasts with most organic chromophores and is widely considered a signature of interchromopohore energy funneling. We apply broad-band ultrafast fluorescence spectroscopy to resolve the evolution of fluorescence spectra for dilute solutions of conjugated oligothiophenes, where no energy transfer is possible. Fluorescence spectra evolve from a mirror image of absorption, which lacks vibronic structure, toward a spectrally narrower and vibronically structured species on the hundreds of femtosecond to early picosecond time scale. Our analysis of this fluorescence spectral evolution shows that a broad distribution of torsional conformers is driven to rapidly planarize in the excited state, including in solid films, which is supported by Raman spectroscopy and quantum chemical modeling. Our data have important implications for understanding different energy-transfer regimes that are delineated by structural relaxation.

Optimization of energy transfer in a polymer composite with perylene chromophores

Luminescent solar concentrators based on molecular dyes are a promising approach to light collection for photovoltaics owing to their potential low cost and wide light acceptance angles. However, they readily suffer from self-absorption, which rapidly reduces device efficiency. We use a perylene-based sensitizer–emitter system to reduce self-absorption. The sensitizer and emitter are copolymerized to enhance energy transfer to the emitter. The sensitizer is susceptible to yield-reducing H-aggregation. We show that a composite polymer can be used to reduce H-aggregation, while maintaining efficient energy transfer.

Capturing ultrafast spectral evolution with transient grating photoluminescence spectroscopy

We have developed a new method, transient grating photoluminescence spectroscopy (TGPLS), allowing the collection of broadband ultrafast photoluminescence spectroscopy with low photoluminescence background. In TGPLS, two ultrafast laser pulses generate a multiplexed transient grating (TG) by the optical Kerr effect. The gated signal is diffracted by the TG and spatially separated from background fluorescence. This high performance nonlinear optical gate delivers time resolution less than 200 fs, spectral bandwidth covering the entire visible region with extremely low fluorescence background. Here we present two applications of TGPLS that provide deeper insight into ultrafast energy transfer in multi-chromophore perylene arrays and ultrafast structural relaxation in oligothiophenes.

Incoherent charge separation dynamics in organic photovoltaics

There is mounting evidence that long-range charge separation determines the efficiency of organic photovoltaic cells, yet different mechanisms remain under debate. One class of proposed mechanism is ultrafast coherent long-range charge separation, and another is a slower process whereby charges incoherently hop apart with a transiently enhanced mobility due to morphology and disorder. Here, we use transient absorption spectroscopy to probe incoherent charge separation dynamics in two different ways. First, we use a family of polymers whose backbone structures allows us to compare 2- phase donor-acceptor morphologies with 3-phase morphologies that feature an intermixed region. In the 3-phase system, we see pronounced spectral signatures associated with charges (holes) occupying the disordered intermixed region, and we track separation via biased charge diffusion to more ordered neat regions on the timescale of hundreds of picoseconds. Secondly, by resolving bimolecular charge recombination at high excitation density, we show that charge mobilities must be substantially enhanced on early timescales, which may be sufficient for separation to occur. Together, these measurements provide support for models of incoherent and relatively slow charge separation.