The maximum open-circuit voltage of a solar cell can be evaluated in terms of its ability to emit light. We herein verify the reciprocity relation between the electroluminescence spectrum and subband-gap quantum efficiency spectrum for several photovoltaic technologies at different stages of commercial development, including inorganic, organic, and a type of methyl-ammonium lead-halide CH 3 NH 3 PbI 3−x Cl x perovskite solar cells. Based on the detailed balance theory and reciprocity relations between light emission and light absorption, voltage losses at open circuit are quantified and assigned to specific mechanisms, namely, absorption edge broadening and nonradiative recombination. The voltage loss due to nonradiative recombination is low for inorganic solar cells (0.04-0.21 V), while for organic solar cell devices it is larger but surprisingly uniform, with values of 0.34-0.44 V for a range of material combinations. We show that, in CH 3 NH 3 PbI 3−x Cl x perovskite solar cells that exhibit hysteresis, the loss to nonradiative recombination varies substantially with voltage scan conditions. We then show that for different solar cell technologies there is a roughly linear relation between the power conversion efficiency and the voltage loss due to nonradiative recombination.
ABSTRACT:The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, in solar cells, higher light-harvesting efficiency leads to higher photocurrent without the need for excellent electrical transport across thick films. We compare extinction coefficients for over 40 conjugated polymers, and find that many different chemical structures share an apparent maximum. In the case of a diketopyrrolopyrrole-thienothiophene copolymer, however, we observe remarkably high optical absorption at relatively low photon energies. We investigate the origin of the optical absorption in terms of backbone structure and conformation using measurements and quantum chemical calculations and find that the high optical absorption can be explained by the high persistence length of the polymer. Accordingly, we demonstrate high absorption in other polymers with high theoretical persistence length. We propose that visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure.2
Systematically moving the alkyl-chain branching position away from the polymer backbone afforded two new thieno[3,2-b]thiophene-diketopyrrolopyrrole (DPPTT-T) polymers. When used as donor materials in polymer:fullerene solar cells, efficiencies exceeding 7% were achieved without the use of processing additives. The effect of the position of the alkyl-chain branching point on the thin-film morphology was investigated using X-ray scattering techniques and the effects on the photovoltaic and charge-transport properties were also studied. For both solar cell and transistor devices, moving the branching point further from the backbone was beneficial. This is the first time that this effect has been shown to improve solar cell performance. Strong evidence is presented for changes in microstructure across the series, which is most likely the cause for the photocurrent enhancement.
In this paper, we provide experimental evidence of the effects of unintentional p-type doping on the performance and the apparent recombination dynamics of bulk-heterojunction solar cells. By supporting these experimental observations with drift-diffusion simulations on two batches of the same efficient polymer-fullerene solar cells with substantially different doping levels and at different thicknesses, we investigate the way the presence of doping affects the interpretation of optoelectronic measurements of recombination and charge transport in organic solar cells. We also present experimental evidence on how unintentional doping can lead to excessively high apparent reaction orders. Our work suggests first that the knowledge of the level of dopants is essential in the studies of recombination dynamics and carrier transport and that unintentional doping levels need to be reduced below approximately 7 × 10 15 cm −3 for full optimization around the second interference maximum of highly efficient polymer-fullerene solar cells.
All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the twodimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20 fs or less.
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