Singlet exciton fission in polycrystalline pentacene: from photophysics toward devices.

Singlet exciton fission is the process in conjugated organic molecules bywhich a photogenerated singlet exciton couples to a nearby chromophore in the ground state, creating a pair of triplet excitons. Researchers first reported this phenomenon in the 1960s, an event that sparked further studies in the following decade. These investigations used fluorescence spectroscopy to establish that exciton fission occurred in single crystals of several acenes.

Control of intrachain charge transfer in model systems for block copolymer photovoltaic materials.

We report the electronic properties of the conjugated coupling between a donor polymer and an acceptor segment serving as a model for the coupling in conjugated donor-acceptor block copolymers. These structures allow the study of possible intrachain photoinduced charge separation, in contrast to the interchain separation achieved in conventional donor-acceptor blends. Depending on the nature of the conjugated linkage, we observe varying degrees of modification of the excited states, including the formation of intrachain charge transfer excitons.

What's God got to do with it? Engaging African-American faith-based institutions in HIV prevention.

African-Americans are disproportionately infected and affected by HIV/AIDS. Although faith-based institutions play critical leadership roles in the African-American community, the faith-based response to HIV/AIDS has historically been lacking. We explore recent successful strategies of a citywide HIV/AIDS awareness and testing campaign developed in partnership with 40 African-American faith-based institutions in Philadelphia, Pennsylvania, a city with some of the USA's highest HIV infection rates.

Charge-Transfer State Dynamics Following Hole and Electron Transfer in Organic Photovoltaic Devices.

The formation of bound electron-hole pairs, also called charge-transfer (CT) states, in organic-based photovoltaic devices is one of the dominant loss mechanisms hindering performance. Whereas CT state dynamics following electron transfer from donor to acceptor have been widely studied, there is not much known about the dynamics of bound CT states produced by hole transfer from the acceptor to the donor. In this letter, we compare the dynamics of CT states formed in the different charge-transfer pathways in a range of model systems.

High internal quantum efficiency in fullerene solar cells based on crosslinked polymer donor networks.

The power conversion efficiency of organic photovoltaic cells depends crucially on the morphology of their donor-acceptor heterostructure. Although tremendous progress has been made to develop new materials that better cover the solar spectrum, this heterostructure is still formed by a primitive spontaneous demixing that is rather sensitive to processing and hence difficult to realize consistently over large areas. Here we report that the desired interpenetrating heterostructure with built-in phase contiguity can be fabricated by acceptor doping into a lightly crosslinked polymer donor network.

Recombination dynamics of charge pairs in a push-pull polyfluorene-derivative.

We investigate the properties of long-lived species in F8BT films through time-resolved photoluminescence (PL) measurements at room temperature and 10 K. The kinetics consist of an initial exponential decay (τ = 2.26 ns) followed by a weak power-law decay (I(t) [proportionality] t(-1)) up to at least 1 ms, both of which depend weakly on temperature.

Aqueous self-assembly of an electroluminescent double-helical metallopolymer.

A new type of water-soluble copper-containing polymer has been synthesized using the technique of subcomponent self-assembly. Copper(I)-directed imine bond formation between triethylene glycol functionalized 1,2-phenylenediamine and 2,9-diformylphenanthroline subcomponents resulted in the formation of a chain in which two conjugated helical ligand strands wrap around a linear array of metal ions. Characterization data from a variety of analytical methods are consistent with our formulation of this material.

On the energetic dependence of charge separation in low-band-gap polymer/fullerene blends.

The energetic driving force required to drive charge separation across donor/acceptor heterojunctions is a key consideration for organic optoelectronic devices. Herein we report a series of transient absorption and photocurrent experiments as a function of excitation wavelength and temperature for two low-band-gap polymer/fullerene blends to study the mechanism of charge separation at the donor/acceptor interface. For the blend that exhibits the smallest donor/acceptor LUMO energy level offset, the photocurrent quantum yield falls as the photon excitation energy is reduced toward the band gap, but the yield of bound, interfacial charge transfer states rises.

Synthesis and photophysics of fully π-conjugated heterobis-functionalized polymeric molecular wires via Suzuki chain-growth polymerization.

We present a fast and efficient in situ synthetic approach to obtain fully π-conjugated polymers with degrees of polymerization up to 23 and near quantitative (>95%) heterobis-functionalization. The synthesis relies on the key advantages of controlled Suzuki chain-growth polymerization: control over molecular weight, narrow polydispersity, and ability to define polymer end groups. The first end group is introduced through the initiator metal complex tBu(3)PPd(X)Br, while the second end group is added by quenching of the chain-growth polymerization with the desired boronic esters.

Direct observation of photoinduced bound charge-pair states at an organic-inorganic semiconductor interface.

It is generally considered that photoinduced charge transfer at the organic-inorganic interfaces in hybrid photovoltaic devices immediately results in a pair of free charge carriers. We extend a novel interface-selective ultrafast "optical pump-push photocurrent probe" technique to study hybrid photovoltaic systems and observe bound electron-hole pair states at the organic-inorganic interface formed between electron-accepting zinc oxide and electron-donating conjugated polymers. We estimate that ∼50% of photogenerated charges stay bound and later recombine, thus hindering the photovoltaic performance of polymer/ZnO cells.

In situ measurement of exciton energy in hybrid singlet-fission solar cells.

Singlet exciton fission-sensitized solar cells have the potential to exceed the Shockley-Queisser limit by generating additional photocurrent from high-energy photons. Pentacene is an organic semiconductor that undergoes efficient singlet fission--the conversion of singlet excitons into pairs of triplets. However, the pentacene triplet is non-emissive, and uncertainty regarding its energy has hindered device design.

Morphology-dependent charge photogeneration in donor-acceptor block copolymer films based on poly(3-hexylthiophene)-block-poly(perylene bisimide acrylate).

We have examined how the nanomorphology and crystallinity of semiconducting double-crystalline block copolymers determine their photophysical and photovoltaic responses. The block copolymers consist of a poly(3-hexylthiophene) (P3HT) donor block coupled to a polymerized perylene bisimide acrylate (PPerAcr) acceptor. Different molecular weights and processing solvents allow the modification of the donor-acceptor interface with regard to their morphology and crystallinity.

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications.

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry.

Highly efficient single-layer polymer ambipolar light-emitting field-effect transistors.

Single-layer polymer light-emitting field-effect transistors (LEFETs) that yield EQEs of >8% and luminance efficiencies >28 cd A(-1) are demonstrated. These values are the highest reported for LEFETs and amongst the highest values for fluorescent OLEDs. Due to the electrostatics of the ambipolar LEFET channel, LEFETs provide an inherent advantage over OLEDs in terms of minimizing exciton-polaron quenching.

Excitons and charges at organic semiconductor heterojunctions.

All-organic heterojunction solar cells now provide very high quantum efficiencies for charge generation and rapidly-improving power conversion efficiencies. Charge generation and separation however, must overcome the strong Coulomb interactions between electrons and holes in these materials that is manifest also through the large exchange energies usually observed. We show for a polymer-polymer system with low charge generation efficiency that this arises through intersystem crossing from the photogenerated charge-transfer state to a lower lying triplet state, mediated by the proton hyperfine interaction, and that the activation barrier for full separation of electrons and holes is of the order of 250 meV.

The role of driving energy and delocalized States for charge separation in organic semiconductors.

The electron-hole pair created via photon absorption in organic photoconversion systems must overcome the Coulomb attraction to achieve long-range charge separation. We show that this process is facilitated through the formation of excited, delocalized band states. In our experiments on organic photovoltaic cells, these states were accessed for a short time (<1 picosecond) via infrared (IR) optical excitation of electron-hole pairs bound at the heterojunction.

On the role of single regiodefects and polydispersity in regioregular poly(3-hexylthiophene): defect distribution, synthesis of defect-free chains, and a simple model for the determination of crystallinity.

Identifying structure formation in semicrystalline conjugated polymers is the fundamental basis to understand electronic processes in these materials. Although correlations between physical properties, structure formation, and device parameters of regioregular, semicrystalline poly(3-hexylthiophene) (P3HT) have been established, it has remained difficult to disentangle the influence of regioregularity, polydispersity, and molecular weight. Here we show that the most commonly used synthetic protocol for the synthesis of P3HT, the living Kumada catalyst transfer polycondensation (KCTP) with Ni(dppp)Cl(2) as the catalyst, leads to regioregular chains with one single tail-to-tail (TT) defect distributed over the whole chain, in contrast to the hitherto assumed exclusive location at the chain end.

Singlet exciton fission-sensitized infrared quantum dot solar cells.

We demonstrate an organic/inorganic hybrid photovoltaic device architecture that uses singlet exciton fission to permit the collection of two electrons per absorbed high-energy photon while simultaneously harvesting low-energy photons. In this solar cell, infrared photons are absorbed using lead sulfide (PbS) nanocrystals. Visible photons are absorbed in pentacene to create singlet excitons, which undergo rapid exciton fission to produce pairs of triplets.

Time-evolution of poly(3-hexylthiophene) as an energy relay dye in dye-sensitized solar cells.

Energy relay dyes (ERD) and Förster resonant energy transfer (FRET) are useful techniques for increasing absorption in dye-sensitized solar cells. We use femtosecond transient absorption spectroscopy to monitor charge generation processes in a solid-state DSC containing poly(3-hexylthiophene) (P3HT) as both the hole-transporter and the ERD with a zinc phthalocyanine dye (TT1) as the sensitizer. We observe efficient FRET occurring on picosecond time scales and subsequent hole transfer from TT1 to P3HT occurring onward from 100 ps.

Collective osmotic shock in ordered materials.

Osmotic shock in a vesicle or cell is the stress build-up and subsequent rupture of the phospholipid membrane that occurs when a relatively high concentration of salt is unable to cross the membrane and instead an inflow of water alleviates the salt concentration gradient. This is a well-known failure mechanism for cells and vesicles (for example, hypotonic shock) and metal alloys (for example, hydrogen embrittlement). We propose the concept of collective osmotic shock, whereby a coordinated explosive fracture resulting from multiplexing the singular effects of osmotic shock at discrete sites within an ordered material results in regular bicontinuous structures.

Solvent additive control of morphology and crystallization in semiconducting polymer blends.

4-bromoanisole is used as a very versatile processing additive to control the phase separation and phase purity of organic photovoltaic devices. Polymer-polymer blends based on P3HT as donor and a wide range of acceptor materials (F8TBT, PCDTBT,…︁) are investigated. The additive promotes the aggregation of P3HT which improves the morphology for both initially mixed and demixed blends.

Ultrafast dynamics of exciton fission in polycrystalline pentacene.

We use ultrafast transient absorption spectroscopy with sub-20 fs time resolution and broad spectral coverage to directly probe the process of exciton fission in polycrystalline thin films of pentacene. We observe that the overwhelming majority of initially photogenerated singlet excitons evolve into triplet excitons on an ∼80 fs time scale independent of the excitation wavelength. This implies that exciton fission occurs at a rate comparable to phonon-mediated exciton localization processes and may proceed directly from the initial, delocalized, state.