Exploring the origin of high optical absorption in conjugated polymers

Vezie, Michelle S. et al.The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compared over 40 conjugated polymers, and found that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we 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. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure.M.S.V. and S. F. are grateful to the Engineering and Physical Sciences Research Council (EPSRC) for a doctoral training award and a CDT studentship (EP/G037515/1) respectively. G.P. and S.C.H. acknowledge the University of Cyprus for funding through the internal grant "ORGANIC". B.D., A.G. and M.C.Q. acknowledge financial support from the Ministerio de Economía y Competitividad of Spain through projects CSD2010–00044 (Consolider NANOTHERM), SEV-2015_0496 and MAT2012–37776 and the European Research Council through project ERC CoG648901. I.M., R.S.A. and I.McC. acknowledge support from the European Commission FP7 Project ArtESun (604397). J.N. is grateful to the Royal Society for a Wolfson Merit Award, and acknowledges financial support from EPSRC grants EP/K030671/1, EP/K029843/1 and EP/J017361/1. The authors thank Dr. Isabel Alonso for performing supplementary ellipsometric measurements; we thank Prof. Thomas Kirchartz, Dr. Jarvist Moore Frost, Dr. Christian Müller and Dr. Isabel Alonso for helpful discussions.Peer reviewe

Understanding the effect of unintentional doping on transport optimization and analysis in efficient organic bulk-heterojunction solar cells

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 × 1015 cm-3 for full optimization around the second interference maximum of highly efficient polymer-fullerene solar cells.F. D. and J. R. D. are thankful of the support from the EPSRC APEX Grant No. EP/H040218/2 and SPECIFIC Grant No. EP/1019278. T. K. acknowledges funding by an Imperial College Junior Research Fellowship. We are grateful to the Ministerio de Economa y Competitividad for funding through the project PHOTOCOMB, Reference No. MAT2012-37776.Peer Reviewe

Do ultrafast exciton-polaron decoherence dynamics govern photocarrier generation efficiencies in polymer 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 two-dimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20\,fs or less

Understanding the Effect of Unintentional Doping on Transport Optimization and Analysis in Efficient Organic Bulk-Heterojunction Solar Cells

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 7×1015  cm−3 for full optimization around the second interference maximum of highly efficient polymer-fullerene solar cells

Quantifying Losses in Open-Circuit Voltage in Solution-Processable Solar Cells

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 CH3NH3PbI3−xClx 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 CH3NH3PbI3−xClx 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

Exploring the origin of high optical absorption in conjugated polymers.

The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compare over 40 conjugated polymers, and find that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we 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. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure

Exploring the origin of high optical absorption in conjugated polymers.

The specific optical absorption of an organic semiconductor is critical to the performance of organic optoelectronic devices. For example, higher light-harvesting efficiency can lead to higher photocurrent in solar cells that are limited by sub-optimal electrical transport. Here, we compare over 40 conjugated polymers, and find that many different chemical structures share an apparent maximum in their extinction coefficients. However, a diketopyrrolopyrrole-thienothiophene copolymer shows remarkably high optical absorption at relatively low photon energies. By investigating its backbone structure and conformation with measurements and quantum chemical calculations, we 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. Visible light harvesting may be enhanced in other conjugated polymers through judicious design of the structure

Impact of Marginal Exciton–Charge-Transfer State Offset on Charge Generation and Recombination in Polymer:Fullerene Solar Cells

The energetic offset between the initial photoexcited state and charge-transfer (CT) state in organic heterojunction solar cells influences both charge generation and open-circuit voltage (Voc). Here, we use time-resolved spectroscopy and voltage loss measurements to analyze the effect of the exciton–CT state offset on charge transfer, separation, and recombination processes in blends of a low-band-gap polymer (INDT-S) with fullerene derivatives of different electron affinity (PCBM and KL). For the lower exciton–CT state offset blend (INDT-S:PCBM), both photocurrent generation and nonradiative voltage losses are lower. The INDT-S:PCBM blend shows different excited-state dynamics depending on whether the donor or acceptor is photoexcited. Surprisingly, the charge recombination dynamics in INDT-S:PCBM are distinctly faster than those in INDT-S:KL upon excitation of the donor. We reconcile these observations using a kinetic model and by considering hybridization between the lowest excitonic and CT states. The modeling results show that this hybridization can significantly reduce Voc losses while still allowing reasonable charge generation efficiency