Polymer nanofibers: preserving nanomorphology in ternary blend organic photovoltaics.

The morphology of donor-acceptor blends holds the key to good performance through the balancing of good exciton dissociation efficiency and interconnectivity for good charge collection. In this work, the good morphology is preserved in ternary blend systems through the use of poly(3-hexylthiophene) (P3HT) nanofibers. The iridium(III)-based metal complex is incorporated in P3HT-PCBM blends as a triplet exciton sensitizer in the bulk heterojunction (BHJ) organic photovoltaics (OPV). The devices using triplet-sensitized ternary blends of P3HT experience a significant degradation in performance, a tendency further aggravated by thermal treatment. This is due to disruption in the morphology thus affecting charge generation and collection. In order to overcome these morphological issues and to circumvent the restriction due to the crystallization of the polymers, here we demonstrate the use of pre-assembled nanofibers in these ternary blends. The concept of stabilizing the nanomorphology of the blend material through the use of nanofibers can also be applied to other ternary systems.

Understanding the role of single molecular ZnS precursors in the synthesis of In(Zn)P/ZnS nanocrystals.

Environmentally friendly nanocrystals (NCs) such as InP are in demand for various applications, such as biomedical labeling, solar cells, sensors, and light-emitting diodes (LEDs). To fulfill their potential applications, the synthesis of such high-quality "green" InP NCs required further improvement so as to achieve better stability, higher brightness NCs, and also to have a more robust synthesis route. The present study addresses our efforts on the synthesis of high-quality In(Zn)P/ZnS core-shell NCs using an air- and moisture-stable ZnS single molecular precursor (SMP) and In(Zn)P cores. The SMP method has recently emerged as a promising route for the surface overcoating of NCs due to its simplicity, high reproducibility, low reaction temperature, and flexibility in controlling the reaction. The synthesis involved heating the In(Zn)P core solution and Zn(S2CNR2) (where R = methyl, ethyl, butyl, or benzyl and referred to as ZDMT, ZDET, ZDBT, or ZDBzT, respectively) in oleylamine (OLA) to 90-250 °C for 0.5-2.5 h. In this work, we systematically studied the influence of different SMP end groups, the complex formation and stability between the SMP and oleylamine (OLA), the reaction temperature, and the amount of SMP on the synthesis of high-quality In(Zn)P/ZnS NCs. We found that thiocarbamate end groups are an important factor contributing to the low-temperature growth of high-quality In(Zn)P/ZnS NCs, as the end groups affect the polarity of the molecules and result in a different steric arrangement. We found that use of SMP with bulky end groups (ZDBzT) results in nanocrystals with higher photoluminescence quantum yield (PL QY) and better dispersibility than those synthesized with SMPs with the shorter alkyl chain groups (ZDMT, ZDET, or ZDBT). At the optimal conditions, the PL QY of red emission In(Zn)P/ZnS NCs is 55 ± 4%, which is one of the highest values reported. On the basis of structural (XAS, XPS, XRD, TEM) and optical characterization, we propose a mechanism for the growth of a ZnS shell on an In(Zn)P core.

Electron transport limitation in P3HT:CdSe nanorods hybrid solar cells.

Hybrid solar cells have the potential to be efficient solar-energy-harvesting devices that can combine the benefits of solution-processable organic materials and the extended absorption offered by inorganic materials. In this work, an understanding of the factors limiting the performance of hybrid solar cells is explored. Through photovoltaic-device characterization correlated with transient absorption spectroscopy measurements, it was found that the interfacial charge transfer between the organic (P3HT) and inorganic (CdSe nanorods) components is not the factor limiting the performance of these solar cells. The insulating original ligands retard the charge recombination between the charge-transfer states across the CdSe-P3HT interface, and this is actually beneficial for charge collection. These cells are, in fact, limited by the subsequent electron collection via CdSe nanoparticles to the electrodes. Hence, the design of a more continuous electron-transport pathway should greatly improve the performance of hybrid solar cells in the future.

Understanding polycarbazole-based polymer:CdSe hybrid solar cells.

We report for the first time the fabrication and characterization of organic-inorganic bulk heterojunction (BHJ) hybrid solar cells made of poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) and pyridine-capped CdSe nanorods. By optimizing both CdSe loading and active layer film thickness, the power conversion efficiencies (PCEs) of PCDTBT:CdSe hybrid solar cells were able to reach 2%, with PCDTBT:CdSe devices displaying an open-circuit voltage (V(OC )) that is 35% higher than P3HT:CdSe devices due to the deeper HOMO level of PCDTBT polymer. The performance of PCDTBT:CdSe devices is limited by its morphology and also its lower LUMO energy offset compared to P3HT:CdSe devices. Hence, the performance of PCDTBT:CdSe solar cells could be further improved by modifying the morphology of the films and also by including an interlayer to generate a built-in voltage to encourage exciton dissociation. Our results suggest that PCDTBT could be a viable alternative to P3HT as an electron donor in hybrid BHJ solar cells for high photovoltage application.

Stability studies of CdSe nanocrystals in an aqueous environment.

In this paper, CdSe nanocrystal dissolution in an aqueous solution was studied. It was found that light is a key factor affecting the dissolution of nanocrystals. In the presence of light, the electrons generated from CdSe nanocrystals reduce water to hydrogen and hydroxide ions (OH-) while photo-generated holes oxidize CdSe to Cd2+ and elemental Se. The dissolution was accelerated in an acidic medium while moderate alkalinity (pH=10.3) can slow down the dissolution possibly due to precipitation of nanocrystals. This study has strong implications for the use of these crystals in aqueous environments (bioimaging and dye-sensitized solar cells).

Understanding the effect of surface chemistry on charge generation and transport in poly (3-hexylthiophene)/CdSe hybrid solar cells.

For hybrid solar cells, interfacial chemistry is one of the most critical factors for good device performance. We have demonstrated that the size of the surface ligands and the dispersion of nanoparticles in the solvent and in the polymer are important criteria in obtaining optimized device performance. The size of the ligands will affect the charge transport at the particle/particle and particle/polymer interfaces and the chemical structures of the ligands will determine their compatibility with the solvent and polymer. Hence other than pyridine, 2-thiophenemethylamine also showed good potential as ligand replacement for poly(3-hexylthiophene)/CdSe hybrid solar cells. With the right ligand combination, we have shown that the power conversion efficiency improved by a factor of 6 after ligand exchange.