Carsten Deibel

Polymer–fullerene bulk heterojunction solar cells

Organic solar cells have the potential to be low-cost and efficient solar energy converters, with a promising energy balance. They are made of carbon-based semiconductors, which exhibit favourable light absorption and charge generation properties, and can be manufactured by low temperature processes such as printing from solvent-based inks, which are compatible with flexible plastic substrates or even paper. In this review, we will present an overview of the physical function of organic solar cells, their state-of-the-art performance and limitations, as well as novel concepts to achieve a better material stability and higher power conversion efficiencies. We will also briefly review processing and cost in view of the market potential.

Role of the charge transfer state in organic donor-acceptor solar cells.

Charge transfer complexes are interfacial charge pairs residing at the donor-acceptor heterointerface in organic solar cell. Experimental evidence shows that it is crucial for the photovoltaic performance, as both photocurrent and open circuit voltage directly depend on it. For charge photogeneration, charge transfer complexes represent the intermediate but essential step between exciton dissotiation and charge extraction. Recombination of free charges to the ground state is via the bound charge transfer state before being lost to the ground state. In terms of the open circuit voltage, its maximum achievable value is determined by the energy of the charge transfer state. An important question is whether or not maximum photocurrent and maximum open circuit voltage can be achieved simultaneously. The impact of increasing the CT energy-in order to raise the open circuit voltage, but lowering the kinetic excess energy of the CT complexes at the same time-on the charge photogeneration will accordingly be discussed. Clearly, the fundamental understanding of the processes involving the charge transfer state is essential for an optimisation of the performance of organic solar cells.

S-shaped current-voltage characteristics of organic solar devices

Measuring the current-voltage characteristic of organic bulk heterojunction solar devices sometimes reveals an S-shaped deformation. We qualitatively produce this behavior by a numerical device simulation assuming a reduced surface recombination. Furthermore we show how to experimentally create these double diodes by applying an oxygen plasma etch on the indium-tin-oxide anode. Restricted charge transport over material interfaces accumulates space charges and therefore creates S-shaped deformations. Finally we discuss the consequences of our findings for the open-circuit voltage Voc.

Origin of the efficient polaron-pair dissociation in polymer-Fullerene blends.

The separation of photogenerated polaron pairs in organic bulk heterojunction solar cells is the intermediate but crucial step between exciton dissociation and charge transport to the electrodes. In state-of-the-art devices, above 80% of all polaron pairs are separated at fields of below 10(7) V/m. In contrast, considering just the Coulomb binding of the polaron pair, electric fields above 10(8) V/m would be needed to reach similar yields. In order to resolve this discrepancy, we performed kinetic Monte Carlo simulations of polaron-pair dissociation in donor-acceptor blends, considering delocalized charge carriers along conjugated polymer chain segments. We show that the resulting fast local charge carrier transport can indeed explain the high experimental quantum yields in polymer solar cells.

Oxygen doping of P3HT:PCBM blends: Influence on trap states, charge carrier mobility and solar cell performance

Abstract We investigated the influence of oxygen on the performance of P3HT:PCBM (poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester) solar cells by current–voltage, thermally stimulated current (TSC) and charge extraction by linearly increasing voltage (CELIV) measurement techniques. The exposure to oxygen leads to an enhanced charge carrier concentration and a decreased charge carrier mobility. Further, an enhanced formation of deeper traps was observed, although the overall density of traps was found to be unaffected upon oxygen exposure. With the aid of macroscopic simulations, based on solving the differential equation system of Poisson, continuity and drift-diffusion equations in one dimension, we demonstrate the influence of a reduced charge carrier mobility and an increased charge carrier density on the main solar cell parameters, consistent with experimental findings.

Radiative efficiency of lead iodide based perovskite solar cells

The maximum efficiency of any solar cell can be evaluated in terms of its corresponding ability to emit light. We herein determine the important figure of merit of radiative efficiency for Methylammonium Lead Iodide perovskite solar cells and, to put in context, relate it to an organic photovoltaic (OPV) model device. We evaluate the reciprocity relation between electroluminescence and photovoltaic quantum efficiency and conclude that the emission from the perovskite devices is dominated by a sharp band-to-band transition that has a radiative efficiency much higher than that of an average OPV device. As a consequence, the perovskite have the benefit of retaining an open circuit voltage ~0.14 V closer to its radiative limit than the OPV cell. Additionally, and in contrast to OPVs, we show that the photoluminescence of the perovskite solar cell is substantially quenched under short circuit conditions in accordance with how an ideal photovoltaic cell should operate.

Trap distribution and the impact of oxygen-induced traps on the charge transport in poly(3-hexylthiophene)

The trap distribution in the conjugated polymer poly(3-hexylthiophene) was investigated by fractional thermally stimulated current measurements. Two defect states with activation energies of about 50 and 105 meV and Gaussian energy distributions were revealed. The first is assigned to the tail of the intrinsic density of states, whereas the concentration of the second trap is directly related to oxygen exposure. The impact of the oxygen induced traps on the charge transport was examined by performing photo-induced charge carrier extraction by linearly increasing voltage measurements that exhibited a strong decrease in the mobility with air exposure time.

Influence of charge carrier mobility on the performance of organic solar cells

The power conversion efficiency of organic solar cells based on donor–acceptor blends is governed by an interplay of polaron pair dissociation and bimolecular polaron recombination. Both processes are strongly dependent on the charge carrier mobility, the dissociation increasing with faster charge transport, with raised recombination losses at the same time. Using a macroscopic effective medium simulation, we calculate the optimum charge carrier mobility for the highest power conversion efficiency, for the first time accounting for injection barriers and a reduced Langevin-type recombination. An enhancement of the charge carrier mobility from 10–8 m2/V s for state of the art polymer–fullerene solar cells to about 10–6 m2/V s, which yields the maximum efficiency, corresponds to an improvement of only about 20% for the given parameter set. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Energetics of excited states in the conjugated polymer poly(3-hexylthiophene)

There is an enormous potential in applying conjugated polymers in novel organic opto-electronic devices such as light emitting diodes and solar cells. Although prototypes and first products exist, a comprehensive understanding of the fundamental processes and energetics involved during photoexcitation is still lacking and limits further device optimisations. Here we report on a unique analysis of the excited states involved in charge generation by photoexcitation. On the model system poly(3-hexylthiophene) (P3HT), we demonstrate the general applicability of our novel approach. From photoemission spectroscopy of occupied and unoccupied states we determine the transport gap to 2.6 eV, which we show to be in agreement with the onset of photoconductivity by spectrally resolved photocurrent measurements. For photogenerated singlet exciton at the absorption edge, 0.7 eV of excess energy are required to overcome the binding energy; the intermediate charge transfer state is situated only 0.3 eV above the singlet exciton. Our results give direct evidence of energy levels involved in the photogeneration and charge transport within conjugated polymers.

Polaron recombination in pristine and annealed bulk heterojunction solar cells

We determined the dominant polaron recombination loss mechanism in pristine and annealed polythiophene:fullerene blend solar cells by applying the photoinduced charge extraction by linearly increasing voltage method in dependence on temperature. In pristine samples, we find a strongly temperature-dependent bimolecular polaron recombination rate, which is reduced as compared to the Langevin theory. For the annealed sample, we observe a polaron decay rate which follows a third order of carrier concentration almost temperature independently.