Perylene Diimide acceptors: Fabrication and characterization of electron-only, hole-only devices and solar cells

The thrust towards energy conservation and reduced environmental footprint has fueled intensive research for alternative low cost sources of renewable energy. Organic photovoltaic cells (OPVs), with their low fabrication costs, easy processing and flexibility, represent a possible viable alternative. Perylene diimides (PDIs) are promising electron-acceptor candidates for bulk heterojunction (BHJ) OPVs, as they combine higher absorption and stability with tunable material properties, such as solubility and position of the lowest unoccupied molecular orbital (LUMO) level. A prerequisite for trap free electron transport is for the LUMO to be located at a level deeper than 3.7 eV since electron trapping in organic semiconductors is universal and dominated by a trap level located at 3.6 eV. Although the mostly used fullerene acceptors in polymer:fullerene solar cells feature trap-free electron transport, low optical absorption of fullerene derivatives limits maximum attainable efficiency. In this thesis, we try to get a better understanding of the electronic properties of PDIs, with a focus on charge carrier transport characteristics and the effect of different processing conditions such as annealing temperature and top contact (cathode) material. We report on a commercially available PDI and three PDI derivatives as acceptor materials, and its blends with MEH-PPV (Poly[2-methoxy 5-(2-ethylhexyloxy)-1,4-phenylenevinylene]) and P3HT (Poly(3-hexylthiophene-2,5-diyl)) donor materials in single carrier devices (electron-only and hole-only) and in solar cells. Space-charge limited current measurements and modelling of temperature dependent J-V characteristics confirmed that the electron transport is essentially trap-free in such materials. Different blend ratios of P3HT:PDI-1 (1:1) and (1:3) show increase in the device performance with increasing PDI-1 ratio. Furthermore, thermal annealing of the devices have a significant effect in the solar cells that decreases open-circuit voltage (Voc) and fill factor FF, but increases short-circuit current (Jsc) and overall device performance. Morphological studies show that over-aggregation in traditional donor:PDI blend systems is still a big problem, which hinders charge carrier transport and performance in solar cells.

Electrokinetic treatment of environmental matrices. Contaminants removal and phosphorus recovery

There is a need to develop viable techniques for removal and recovery organic and inorganic compounds from environmental matrices, due to their ecotoxicity, regulatory obligations or potential supplies as secondary materials. In this dissertation, electro –removal and –recovery techniques were applied to five different contaminated environmental matrices aiming phosphorus (P) recovery and/or contaminants removal. In a first phase, the electrokinetic process (EK) was carried out in soils for (i) metalloids and (ii) organic contaminants (OCs) removal. In the case of As and Sb mine contaminated soil, the EK process was additionally coupled with phytotechnologies. In a second phase, the electrodialytic process (ED) was applied to wastes aiming P recovery and simultaneous removal of (iii) toxins from membrane concentrate, (iv) heavy metals from sewage sludge ash (SSA), and (v) OCs from sewage sludge (SS). EK enhanced phytoremediation showed to be viable for the remediation of soils contaminated with metalloids, as although remediation was low, it combines advantages of both technologies while allowing site management. EK also proved to be an effective remediation technology for the removal and degradation of emerging OCs from two types of soil. Aiming P recovery and contaminants removal, different ED cell set-ups were tested. For the membrane concentrates, the best P recovery was achieved in a three compartment (3c) cell, but the highest toxin removal was obtained in a two compartment (2c) cell, placing the matrix in the cathode end. In the case of SSA the best approach for simultaneous P recovery and heavy metals removal was to use a 2c-cell placing the matrix in the anode end. However, for simultaneous P recovery and OCs removal, SS should be placed in the cathode end, in a 2c-cell. Overall, the data support that the selection of the cell design should be done case-by-case.