Ines Dumsch

On the Field Dependence of Free Charge Carrier Generation and Recombination in Blends of PCPDTBT/PC70BM: Influence of Solvent Additives

We have applied time-delayed collection field (TDCF) and charge extraction by linearly increasing voltage (CELIV) to investigate the photogeneration, transport, and recombination of charge carriers in blends composed of PCPDTBT/PC70BM processed with and without the solvent additive diiodooctane. The results suggest that the solvent additive has severe impacts on the elementary processes involved in the photon to collected electron conversion in these blends. First, a pronounced field dependence of the free carrier generation is found for both blends, where the field dependence is stronger without the additive. Second, the fate of charge carriers in both blends can be described with a rather high bimolecular recombination coefficients, which increase with decreasing internal field. Third, the mobility is three to four times higher with the additive. Both blends show a negative field dependence of mobility, which we suggest to cause bias-dependent recombination coefficients.

Structural correlations in the generation of polaron pairs in low-bandgap polymers for photovoltaics

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (η=8%). π-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.

Quantifying Charge Extraction in Organic Solar Cells: The Case of Fluorinated PCPDTBT

We introduce a new and simple method to quantify the effective extraction mobility in organic solar cells at low electric fields and charge carrier densities comparable to operation conditions under one sun illumination. By comparing steady-state carrier densities at constant illumination intensity and under open-circuit conditions, the gradient of the quasi-Fermi potential driving the current is estimated as a function of external bias and charge density. These properties are then related to the respective steady-state current to determine the effective extraction mobility. The new technique is applied to different derivatives of the well-known low-band-gap polymer PCPDTBT blended with PC70BM. We show that the slower average extraction due to lower mobility accounts for the moderate fill factor when solar cells are fabricated with mono- or difluorinated PCPDTBT. This lower extraction competes with improved generation and reduced nongeminate recombination, rendering the monofluorinated derivative the most efficient donor polymer.

How intermolecular geometrical disorder affects the molecular doping of donor-acceptor copolymers

Molecular doping of conjugated polymers represents an important strategy for improving organic electronic devices. However, the widely reported low efficiency of doping remains a crucial limitation to obtain high performance. Here we investigate how charge transfer between dopant and donor-acceptor copolymers is affected by the spatial arrangement of the dopant molecule with respect to the copolymer repeat unit. We p-dope a donor-acceptor copolymer and probe its charge-sensitive molecular vibrations in films by infrared spectroscopy. We find that, compared with a related homopolymer, a four times higher dopant/polymer molar ratio is needed to observe signatures of charges. By DFT methods, we simulate the vibrational spectra, moving the dopant along the copolymer backbone and finding that efficient charge transfer occurs only when the dopant is close to the donor moiety. Our results show that the donor-acceptor structure poses an obstacle to efficient doping, with the acceptor moiety being inactive for p-type doping.

Photo-induced charge recombination kinetics in low bandgap PCPDTBT polymer:CdSe quantum dot bulk heterojunction solar cells

The interfacial charge transfer recombination processes under working conditions that limit the device performance in polymer:CdSe quantum dot bulk heterojunction hybrid solar cells have been measured. The recombination lifetimes for electrons and holes in the device show an exponential dependence in a similar way to that observed for other molecular based solar cells such as bulk heterojunction organic solar cells (OSC) and dye sensitized solar cells (DSSC). The implications of this unprecedented observation on the design of novel devices are discussed as well as the relationship between the charge accumulation in these devices under operation and the device open-circuit voltage.

Electric Field Distribution in Hybrid Solar Cells Comprising an Organic Donor Polymer and Amorphous Silicon

Abstract We present a study on the performance and analysis of hybrid solar cells comprising a planar heterojunction between between a conjugated donor polymer, P3HT or PCPDTBT, and hydrogenated amorphous silicon (a-Si:H). A comparison of the modeled absorption spectra of the layer stack with the measured external quantum efficiency is used to investigate the contribution of the inorganic and organic material to the photocurrent generation in the device. Although both materials contribute to the photocurrent, the devices exhibit poor quantum efficiencies and low short circuit currents. Bandstructure simulations of the hybrid layer structure reveal that an unfavorable electric field distribution within the planar multilayer structure limits the performance. Using electroabsorption measurements we can show that the electric field is extremelyweak in the amorphous silicon but strong in the organic material. The situation changes drasticallywhen the conjugated polymer is p-doped. Doping not only increases the conductivity of the organic material, but also restores the electric field in the amorphous silicon layer. Optimized hybrid solar cells comprising thin doped P3HT layers exhibit energy conversion efficiencies (ECE) up to 2.8 %.