Morphological, Chemical, and Electronic Changes of the Conjugated Polymer PTB7 with Thermal Annealing.

There is considerable interest in improving the performance of organic optoelectronic devices through processing techniques. Here, we study the effect of high-temperature annealing on the properties of the semiconducting polymer PTB7 and PTB7:fullerene blends, of interest as efficient organic photovoltaic (OPV) devices. Annealing to moderate temperature improves the PTB7 morphology and optoelectronic properties. High-temperature annealing also improves morphology but results in poorer optoelectronic properties. This is a result of side chain cleavage that creates by-products that act as trap states, increasing electronic disorder and decreasing mobility. We further observe changes to the PTB7 chemical structure after thermal cleavage that are similar to those following solar irradiation. This implies that side chain cleavage is an important mechanism in device photodegradation, which is a major "burn-in" loss mechanism in OPV. These results lend insight into side chain cleavage as a method of improving optoelectronic properties and suggest strategies for improvement in device photostability.

Langmuir-Blodgett Thin Films of Diketopyrrolopyrrole-Based Amphiphiles.

We report on two π-conjugated donor-acceptor-donor (D-A-D) molecules of amphiphilic nature, aiming to promote intermolecular ordering and carrier mobility in organic electronic devices. Diketopyrrolopyrrole was selected as the acceptor moiety that was disubstituted with nonpolar and polar functional groups, thereby providing the amphiphilic structures. This structural design resulted in materials with a strong intermolecular order in the solid state, which was confirmed by differential scanning calorimetry and polarized optical microscopy. Langmuir-Blodgett (LB) films of ordered mono- and multilayers were transferred onto glass and silicon substrates, with layer quality, coverage, and intermolecular order controlled by layer compression pressure on the LB trough. Organic field-effect transistors and organic photovoltaics devices with active layers consisting of the amphiphilic conjugated D-A-D-type molecules were constructed to demonstrate that the LB technique is an effective layer-by-layer deposition approach to fabricate self-assembled, ordered thin films.

Kinetic Versus Thermodynamic Orientational Preferences for a Series of Isomorphic Molecular Semiconductors.

Due to the anisotropic nature of charge transport through most organic semiconductors, the orientation of the conjugated backbone is of great relevance because it may affect final device properties. Herein, we present a set of four nearly isostructural molecular organic semiconducting materials whose orientation changes drastically with a two-atom change in the conjugated framework. We investigate the X-ray diffraction patterns of these materials in the thin film, both as-deposited from solution and following melt-annealing. Following melt-annealing of the films, crystallites of all four materials orient edge-on with respect to the substrate, which indicates that this orientation is thermodynamically preferred. We can infer that the initial face-on orientation of some of the materials is due to kinetic trapping during the spin-coating process. Previous observations from the literature suggest that the edge-on orientation is the thermodynamically preferable state for many organic semiconducting materials. However, a cohesive explanation for this phenomenon remains elusive.

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer.

The influence of various processing conditions on the singlet exciton diffusion is explored in films of a conjugated random copolymer poly-(3-hexylthiophene-co-3-dodecylthiophene) (P3HT-co-P3DDT) and correlated with the degree of crystallinity probed by grazing incidence X-ray scattering and with exciton bandwidth determined from absorption spectra. The exciton diffusion coefficient is deduced from exciton-exciton annihilation measurements and is found to increase by more than a factor of three when thin films are annealed using CS2 solvent vapour. A doubling of exciton diffusion coefficient is observed upon melt annealing at 200 °C and the corresponding films show about 50% enhancement in the degree of crystallinity. In contrast, films fabricated from polymer solutions containing a small amount of either solvent additive or nucleating agent show a decrease in exciton diffusion coefficient possibly due to formation of traps for excitons. Our results suggest that the enhancement of exciton diffusivity occurs because of increased crystallinity of alkyl-stacking and longer conjugation of aggregated chains which reduces the exciton bandwidth.

Semi-random vs Well-Defined Alternating Donor-Acceptor Copolymers.

The influence of backbone composition on the physical properties of donor-acceptor (D-A) copolymers composed of varying amounts of benzodithiophene (BDT) donor with the thienoisoindoledione (TID) acceptor is investigated. First, the synthesis of bis- and tris-BDT monomers is reported; these monomers are subsequently used in Stille copolymerizations to create well-defined alternating polymer structures with repeating (D-A), (D-D-A), and (D-D-D-A) units. For comparison, five semi-random D-A copolymers with a D:A ratio of 1.5, 2, 3, 4, and 7 were synthesized by reacting trimethyltin-functionalized BDT with various ratios of iodinated BDT and brominated TID. While the HOMO levels of all the resultant polymers are very similar, a systematic red shift in the absorbance spectra onset of the D-A copolymer films from 687 to 883 nm is observed with increasing acceptor content, suggesting the LUMO can be fine-tuned over a range of 0.4 eV. When the solid-state absorbance spectra of well-defined alternating copolymers are compared to those of semi-random copolymers with analogous D:A ratios, the spectra of the alternating copolymers are significantly more red-shifted. Organic photovoltaic device efficiencies show that the semi-random materials all outperform the well-defined alternating copolymers, and an optimal D:A ratio of 2 produces the highest efficiency. Additional considerations concerning fine-tuning the lifetimes of the photoconductance transients of copolymer:fullerene films measured by time-resolved microwave conductivity are discussed. Overall, the results of this work indicate that the semi-random approach is a powerful synthetic strategy for fine-tuning the optoelectronic and photophysical properties of D-A materials for a number of systematic studies, especially given the ease with which the D:A ratios in the semi-random copolymers can be tuned.

The effect of three-dimensional morphology on the efficiency of hybrid polymer solar cells.

The efficiency of polymer solar cells critically depends on the intimacy of mixing of the donor and acceptor semiconductors used in these devices to create charges and on the presence of unhindered percolation pathways in the individual components to transport holes and electrons. The visualization of these bulk heterojunction morphologies in three dimensions has been challenging and has hampered progress in this area. Here, we spatially resolve the morphology of 2%-efficient hybrid solar cells consisting of poly(3-hexylthiophene) as the donor and ZnO as the acceptor in the nanometre range by electron tomography. The morphology is statistically analysed for spherical contact distance and percolation pathways. Together with solving the three-dimensional exciton-diffusion equation, a consistent and quantitative correlation between solar-cell performance, photophysical data and the three-dimensional morphology has been obtained for devices with different layer thicknesses that enables differentiating between generation and transport as limiting factors to performance.