Oleg V. Kozlov

Bulk heterojunction morphology of polymer: fullerene blends revealed by ultrafast spectroscopy

Morphology of organic photovoltaic bulk heterojunctions (BHJs) – a nanoscale texture of the donor and acceptor phases – is one of the key factors influencing efficiency of organic solar cells. Detailed knowledge of the morphology is hampered by the fact that it is notoriously difficult to investigate by microscopic methods. Here we all-optically track the exciton harvesting dynamics in the fullerene acceptor phase from which subdivision of the fullerene domain sizes into the mixed phase (2–15 nm) and large (>50 nm) domains is readily obtained via the Monte-Carlo simulations. These results were independently confirmed by a combination of X-ray scattering, electron and atomic-force microscopies, and time-resolved photoluminescence spectroscopy. In the large domains, the excitons are lost due to the high energy disorder while in the ordered materials the excitons are harvested with high efficiency even from the domains as large as 100 nm due to the absence of low-energy traps. Therefore, optimizing of blend nanomorphology together with increasing the material order are deemed as winning strategies in the exciton harvesting optimization.

Luminescent Organic Semiconducting Langmuir Monolayers

In recent years, monolayer organic field-effect devices such as transistors and sensors have demonstrated their high potential. In contrast, monolayer electroluminescent organic field-effect devices are still in their infancy. One of the key challenges here is to create an organic material that self-organizes in a monolayer and combines efficient charge transport with luminescence. Herein, we report a novel organosilicon derivative of oligothiophene-phenylene dimer D2-Und-PTTP-TMS (D2, tetramethyldisiloxane; Und, undecylenic spacer; P, 1,4-phenylene; T, 2,5-thiophene; TMS, trimethylsilyl) that meets these requirements. The self-assembled Langmuir monolayers of the dimer were investigated by steady-state and time-resolved photoluminescence spectroscopy, atomic force microscopy, X-ray reflectometry, and grazing-incidence X-ray diffraction, and their semiconducting properties were evaluated in organic field-effect transistors. We found that the best uniform, fully covered, highly ordered monolayers were semiconducting. Thus, the ordered two-dimensional (2D) packing of conjugated organic molecules in the semiconducting Langmuir monolayer is compatible with its high-yield luminescence, so that 2D molecular aggregation per se does not preclude highly luminescent properties. Our findings pave the way to the rational design of functional materials for monolayer organic light-emitting transistors and other optoelectronic devices.

Ultrafast electron and hole transfer in bulk heterojunctions of low-bandgap polymers

Abstract In modern bulk heterojunction (BHJ) organic solar cells, blends of low-bandgap polymer and [70]PCBM acceptor are used in the active layer. In this combination, the polymer absorbs photons from the red and near-IR parts of the solar spectrum, while the blue and near-UV photons are harvested by [70]PCBM. As a result, both electron transfer from polymer to [70]PCBM and hole transfer from [70]PCBM to polymer are of utmost importance in free charge generation and have to be optimized simultaneously. Here we study electron and hole transfer processes in BHJ blends of two low-bandgap polymers, BTT-DPP and PCPDTBT, by ultrafast photoinduced spectroscopy (PIA). By tracking the PIA dynamics, we observed substantially different charge separation pathways in BHJs of the two polymers with [70]PCBM. From the photoinduced anisotropy dynamics, we demonstrated that in the PCPDTBT:[70]PCBM system both electron and hole transfer processes are highly efficient, while in the BTTBPP:[ 70]PCBM electron transfer is blocked due to the unfortunate energy level alignment leaving hole transfer the only pathway to free charge generation. Calculations at the density functional theory level are used to gain more insight into our findings. The presented results highlight the importance of the energy level alignment on the charge separation process. Graphical Abstract

Triphenylamine-Based Push-Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics

Small push–pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs.

Visualization of molecular excitons diffusion

Small organic molecules of the push-pull architecture are rapidly gaining their status in the organic electronics applications. In densely packed molecular films, both intra- and intermolecular interactions play an essential role for the device performance. Here we study two different molecules, a highly symmetric star-shaped one and its newly synthesized single arm analogue, for their photophysical properties. Both chromophores were dissolved in a solid matrix at different concentrations to vary their separation and therefore intermolecular coupling. We show that in both molecules the population relaxation accelerates by more than a factor of 10 at shorter intermolecular distances due to self-quenching thereby reducing the exciton survival time. The transient anisotropy dynamics are also quite similar, with their substantial acceleration at shorter interchromophore distances due to exciton diffusion caused by the Förster-like resonance energy transfer. However, the anisotropy values are noticeably lower for the star-shaped molecule because of intramolecular mixing of different polarization states. Finally, a model is presented that accounts for the observed results.

Ultrafast Electron and Hole Dynamics in Novel Conjugated Star-Shaped Molecules

Charge dynamics in organic photovoltaic blends based on novel star-shaped molecules are studied by ultrafast visible-IR spectroscopy. Pathways of intra- and intermolecular electron and hole transfer and their recombination are identified and discussed.