Synergies and compromises between charge and energy transfers in three-component organic solar cells.

In this paper, we developed different three-component organic heterojunction structures supported by PET/ITO substrates with the aim to study the possible synergies and/or compromises between charge transfer (CT) and energy transfer (ET) processes in organic solar cells (OSCs). As components, we employed poly(3-hexylthiophene-2,5-diyl) (P3HT; donor), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM; acceptor) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) that is known to give good ET to P3HT. At first, we observed that in a planar heterojunction (PHJ) solar cell, F8BT has to be properly located in between P3HT and PCBM to get a cascade energy level configuration allowing for a better CT and power conversion efficiency. Then, we observed that by producing a P3HT:F8BT blend, the energy transfer process can be improved in the P3HT:F8BT/PCBM active layer. This may enable decreasing the thickness of the active layer while maintaining a similar PCE that is very interesting for the development of transparent OSCs. However, the P3HT:F8BT blend limits the P3HT-PCBM CT with respect to a P3HT/F8BT/PCBM PHJ, showing that a compromise between CT and ET is needed to get a higher PCE or higher transparency. By the above approach, in this paper, we developed highly transparent heterojunction structures for solar cell devices with PCEs comparable to those observed from the colorful reference P3HT/PCBM PHJ solar cells on PET/ITO substrates.

Exploring the interplay between ligand derivatisation and cation type in the assembly of hybrid polyoxometalate Mn-Andersons.

Herein a library of hybrid Mn-Anderson polyoxometalates anions are presented: 1, [(MnMo6 O18 )((OCH2 )3 -C-(CH2 )7 CHCH2 )2 ](3-) ; compound 2, [(MnMo6 O18 )((OCH2 )3 C-NHCH2 C16 H9 )2 ](3-) ; compound 3, [(MnMo6 O18 )((OCH2 )3 C-(CH2 )7 CHCH2 )1 ((OCH2 )3 C-NHCH2 C16 H9 )1 ](3-) ; compound 4, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)CH2 CHCH2 )2 ](3-) and compounds 5-9, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)(CH2 )x CH3 )2 ]), where x = 4, 10, 12, 14, and 18 respectively. The compounds resulting from the cation exchange of the anions 1-9 to give TBA (a) and DMDOA (b) salts, and additionally for compounds 1, 2 and 3, tetraphenylphosphonium (PPh4 ) (c) salts, are explored at the air/water interface using scanning force microscopy, showing a range of architectures including hexagonal structures, nanofibers and other supramolecular forms. Additionally the solid-state structures for compounds 1c, 2c, 4a, 6a, 9a, are presented for the first time and these investigations demonstrate the delicate interplay between the structure of the covalently derivatised hybrid organo-clusters as well as the ion-exchange cation types.

Self-organization and nanostructural control in thin film heterojunctions.

In spite of more than two-decades of studies of molecular self-assembly, the achievement of low cost, easy-to-implement and multi-parameter bottom-up approaches to address the supramolecular morphology in three-dimensional (3D) systems is still missing. In the particular case of molecular thin films, the 3D nanoscale morphology and function are crucial for both fundamental and applied research. Here we show how it is possible to tune the 3D film structure (domain size, branching, etc.) of thin film heterojunctions with nanoscale accuracy together with the modulation of their optoelectronic properties by employing an easy two-step approach. At first we prepared multi-planar heterojunctions with a programmed sequence of nanoscopic layers. In a second step, thermal stimuli have been employed to induce the formation of bulk heterojunctions with bicontinuous and interdigitated phases having a size below the exciton diffusion length. Importantly, the study of luminescence quenching of these systems can be considered as a useful means for the accurate estimation of the exciton diffusion length of semiconductors in nanoscale blends. Finally, nearly a thousand times lower material consumption than spin coating allows a drastic reduction of material wasting and a low-cost implementation, besides the considerable possibility of preparing thin film blends also by employing materials soluble in different solvents.