The need to develop inexpensive renewable energy sources stimulates scientific research for efficient, low-cost photovoltaic devices.1 The organic, polymer-based photovoltaic elements have introduced at least the potential of obtaining cheap and easy methods to produce energy from light.2 The possibility of chemically manipulating the material properties of polymers (plastics) combined with a variety of easy and cheap processing techniques has made polymer-based materials present in almost every aspect of modern society.3 Organic semiconductors have several advantages: (a) lowcost synthesis, and (b) easy manufacture of thin film devices by vacuum evaporation/sublimation or solution cast or printing technologies. Furthermore, organic semiconductor thin films may show high absorption coefficients4 exceeding 105 cm-1, which makes them good chromophores for optoelectronic applications. The electronic band gap of organic semiconductors can be engineered by chemical synthesis for simple color changing of light emitting diodes (LEDs).5 Charge carrier mobilities as high as 10 cm2/V‚s6 made them competitive with amorphous silicon.7 This review is organized as follows. In the first part, we will give a general introduction to the materials, production techniques, working principles, critical parameters, and stability of the organic solar cells. In the second part, we will focus on conjugated polymer/fullerene bulk heterojunction solar cells, mainly on polyphenylenevinylene (PPV) derivatives/(1-(3-methoxycarbonyl) propyl-1-phenyl[6,6]C61) (PCBM) fullerene derivatives and poly(3-hexylthiophene) (P3HT)/PCBM systems. In the third part, we will discuss the alternative approaches such as polymer/polymer solar cells and organic/inorganic hybrid solar cells. In the fourth part, we will suggest possible routes for further improvements and finish with some conclusions. The different papers mentioned in the text have been chosen for didactical purposes and cannot reflect the chronology of the research field nor have a claim of completeness. The further interested reader is referred to the vast amount of quality papers published in this field during the past decade.

Conjugated polymer-based organic solar cells

The inherent flexibility afforded by molecular design has accelerated the development of a wide variety of organic semiconductors over the past two decades. In particular, great advances have been made in the development of materials for organic light-emitting diodes (OLEDs), from early devices based on fluorescent molecules to those using phosphorescent molecules. In OLEDs, electrically injected charge carriers recombine to form singlet and triplet excitons in a 1:3 ratio; the use of phosphorescent metal-organic complexes exploits the normally non-radiative triplet excitons and so enhances the overall electroluminescence efficiency. Here we report a class of metal-free organic electroluminescent molecules in which the energy gap between the singlet and triplet excited states is minimized by design, thereby promoting highly efficient spin up-conversion from non-radiative triplet states to radiative singlet states while maintaining high radiative decay rates, of more than 10(6) decays per second. In other words, these molecules harness both singlet and triplet excitons for light emission through fluorescence decay channels, leading to an intrinsic fluorescence efficiency in excess of 90 per cent and a very high external electroluminescence efficiency, of more than 19 per cent, which is comparable to that achieved in high-efficiency phosphorescence-based OLEDs.

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Highly efficient organic light-emitting diodes from delayed fluorescence

Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Polymer-based organic photovoltaic systems hold the promise for a cost-effective, lightweight solar energy conversion platform, which could benefit from simple solution processing of the active layer. The function of such excitonic solar cells is based on photoinduced electron transfer from a donor to an acceptor. Fullerenes have become the ubiquitous acceptors because of their high electron affinity and ability to transport charge effectively. The most effective solar cells have been made from bicontinuous polymer–fullerene composites, or so-called bulk heterojunctions. The best solar cells currently achieve an efficiency of about 5 %, thus significant advances in the fundamental understanding of the complex interplay between the active layer morphology and electronic properties are required if this technology is to find viable application.

Polymer–Fullerene Composite Solar Cells

Solution-processed bulk-heterojunction solar cells have gained serious attention during the last few years and are becoming established as one of the future photovoltaic technologies for low-cost power production. This article reviews the highlights of the last few years, and summarizes today's state-of-the-art performance. An outlook is given on relevant future materials and technologies that have the potential to guide this young photovoltaic technology towards the magic 10% regime. A cost model supplements the technical discussions, with practical aspects any photovoltaic technology needs to fulfil, and answers to the question as to whether low module costs can compensate lower lifetimes and performances.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/adma.200801283

Polymer‐Fullerene Bulk‐Heterojunction Solar Cells

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Principles Of Fluorescence Spectroscopy

The absorption spectrum of polythiophene and its derivative poly(3-hexylthiophene) (P3HT) is usually described in terms of an intrachain exciton coupled to a single phonon mode. We show that this model is too simplistic for highly ordered, regioregular P3HT and that, analogous to the case of charged polarons in this material, interchain interactions must be taken into account to correctly describe the absorption spectrum. We show that the lowest energy feature in the $\ensuremath{\pi}\ensuremath{-}{\ensuremath{\pi}}^{*}$ region of the absorption spectrum is associated with an interchain absorption, the intensity of which is correlated with the degree of order in the polymer. Correspondingly, we show that the emission from P3HT also exhibits contributions from both interchain and intrachain states, in a manner similar to that recently shown for poly(phenylenevinylene). Having reinterpreted the physical origin of the features in the absorption and emission spectra of P3HT, we then model these spectra and show how they evolve as the degree of order in the polymer is changed by varying several physical parameters including temperature and regioregularity of the polymer.

/pdf/effect-of-interchain-interactions-on-the-absorption-and-2sduoac9ok.pdf

Effect of interchain interactions on the absorption and emission of poly(3-hexylthiophene)

Modern optoelectronic devices, such as light-emitting diodes, field-effect transistors and organic solar cells require well controlled motion of charges for their efficient operation. The understanding of the processes that determine charge transport is therefore of paramount importance for designing materials with improved structure-property relationships. Before discussing different regimes of charge transport in organic semiconductors, we present a brief introduction into the conceptual framework in which we interpret the relevant photophysical processes. That is, we compare a molecular picture of electronic excitations against the Su-Schrieffer-Heeger semiconductor band model. After a brief description of experimental techniques needed to measure charge mobilities, we then elaborate on the parameters controlling charge transport in technologically relevant materials. Thus, we consider the influences of electronic coupling between molecular units, disorder, polaronic effects and space charge. A particular focus is given to the recent progress made in understanding charge transport on short time scales and short length scales. The mechanism for charge injection is briefly addressed towards the end of this chapter.

/pdf/charge-transport-in-organic-semiconductors-ecbvuiimvi.pdf

Charge transport in organic semiconductors.

Today's technology is not possible without optoelectronic devices such as light-emitting diodes, transistors and solar cells. These basic units of modern electronic appliances may be made not only from traditional inorganic semiconductors, but also from organic semiconductors, i.e. hydrocarbon molecules that combine semiconducting properties with some mechanical properties such as easy processability and flexibility. The weak van der Waals forces that bind the molecules to a solid imply a low dielectric constant, so that coulomb and exchange interactions between electrons are significant. As a result, photoexcitation or electrical excitation results in strongly bound electron–hole pairs, so-called excitons. Depending on the relative orientation of the electron and hole spin, the exciton may be of a overall singlet or triplet spin state. While the fluorescent singlet state has been investigated intensively since the first reports of organic electroluminescence, research into the properties of the phosphorescent triplet state has intensified mainly during the last decade. In this review we give an overview on the photophysical processes associated with the formation of triplet states and their decay, as well as the energy levels and energy transfer processes of triplet states. We aim to give a careful introduction for those new to this particular research area as well as to highlight some of the current research issues and intriguing questions for those familiar with the field. The main focus of this review is on molecular assemblies and polymer films, though relevant work on molecular crystals is also included where it assists in forming a larger picture.

Triplet states in organic semiconductors

The migration and accumulation of iodide ions create a modulation of the respective interfacial barriers causing the hysteresis in solar cells based on methylammonium lead iodide perovskites. Iodide ions are identified as the migrating species by measuring temperature dependent current-transients and photoelectron spectroscopy. The involved changes in the built-in potential due to ion migration are directly measured by electroabsorption spectroscopy.

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Iodine Migration and its Effect on Hysteresis in Perovskite Solar Cells.

The efficiency of light-emitting diodes (LEDs) made from organic semiconductors is determined by the fraction of injected electrons and holes that recombine to form emissive spin-singlet states rather than non-emissive spin-triplet states. If the process by which these states form is spin-independent, the maximum efficiency of organic LEDs will be limited to 25 per cent1. But recent reports have indicated fractions of emissive singlet states ranging from 22 to 63 per cent2,3,4,5, and the reason for this variation remains unclear. Here we determine the absolute fraction of singlet states generated in a platinum-containing conjugated polymer and its corresponding monomer. The spin-orbit coupling introduced by the platinum atom allows triplet-state emission, so optically and electrically generated luminescence from both singlet and triplet states can be compared directly. We find an average singlet generation fraction of 22 ± 1 per cent for the monomer, but 57 ± 4 per cent for the polymer. This suggests that recombination is spin-independent for the monomer, but that a spin-dependent process, favouring singlet formation, is effective in the polymer. We suggest that this process is a consequence of the exchange interaction, which will operate on overlapping electron and hole wavefunctions on the same polymer chain at their capture radius.

/pdf/spin-dependent-exciton-formation-in-p-conjugated-compounds-2uf6ovgq2o.pdf

Anna Köhler

Papers

Effect of interchain interactions on the absorption and emission of poly(3-hexylthiophene)

Charge transport in organic semiconductors.

Triplet states in organic semiconductors

Iodine Migration and its Effect on Hysteresis in Perovskite Solar Cells.

Spin-dependent exciton formation in π-conjugated compounds