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

There has been an intensive search for cost-effective photovoltaics since the development of the first solar cells in the 1950s. [1–3] Among all alternative technologies to silicon-based pn-junction solar cells, organic solar cells could lead the most significant cost reduction. [4] The field of organic photovoltaics (OPVs) comprises organic/inorganic nanostructures like dyesensitized solar cells, multilayers of small organic molecules, and phase-separated mixtures of organic materials (the bulkheterojunction solar cell). A review of several OPV technologies has been presented recently. [5] Light absorption in organic solar cells leads to the generation of excited, bound electron– hole pairs (often called excitons). To achieve substantial energy-conversion efficiencies, these excited electron–hole pairs need to be dissociated into free charge carriers with a high yield. Excitons can be dissociated at interfaces of materials with different electron affinities or by electric fields, or the dissociation can be trap or impurity assisted. Blending conjugated polymers with high-electron-affinity molecules like C60 (as in the bulk-heterojunction solar cell) has proven to be an efficient way for rapid exciton dissociation. Conjugated polymer–C60 interpenetrating networks exhibit ultrafast charge transfer (∼40 fs). [6,7] As there is no competing decay process of the optically excited electron–hole pair located on the polymer in this time regime, an optimized mixture with C60 converts absorbed photons to electrons with an efficiency close to 100%. [8] The associated bicontinuous interpenetrating network enables efficient collection of the separated charges at the electrodes. The bulk-heterojunction solar cell has attracted a lot of attention because of its potential to be a true low-cost photovoltaic technology. A simple coating or printing process would enable roll-to-roll manufacturing of flexible, low-weight PV modules, which should permit cost-efficient production and the development of products for new markets, e.g., in the field of portable electronics. One major obstacle for the commercialization of bulk-heterojunction solar cells is the relatively small device efficiencies that have been demonstrated up to now. [5] The best energy-conversion efficiencies published for small-area devices approach 5%. [9–11] A detailed analysis of state-of-the-art bulk-heterojunction solar cells [8] reveals that the efficiency is limited by the low opencircuit voltage (Voc) delivered by these devices under illumination. Typically, organic semiconductors with a bandgap of about 2 eV are applied as photoactive materials, but the observed open-circuit voltages are only in the range of 0.5–1 V. There has long been a controversy about the origin of the Voc in conjugated polymer–fullerene solar cells. Following the classical thin-film solar-cell concept, the metal–insulator–metal (MIM) model was applied to bulk-heterojunction devices. In the MIM picture, Voc is simply equal to the work-function difference of the two metal electrodes. The model had to be modified after the observation of the strong influence of the reduction potential of the fullerene on the open-circuit volt

Design Rules for Donors in Bulk‐Heterojunction Solar Cells—Towards 10 % Energy‐Conversion Efficiency

Organic solar cell research has developed during the past 30 years, but especially in the last decade it has attracted scientific and economic interest triggered by a rapid increase in power conversion efficiencies. This was achieved by the introduction of new materials, improved materials engineering, and more sophisticated device structures. Today, solar power conversion efficiencies in excess of 3% have been accomplished with several device concepts. Though efficiencies of these thin-film organicdevices have not yet reached those of their inorganic counterparts (η ≈ 10–20%); the perspective of cheap production (employing, e.g., roll-to-roll processes) drives the development of organic photovoltaic devices further in a dynamic way. The two competitive production techniques used today are either wet solution processing or dry thermal evaporation of the organic constituents. The field of organic solar cells profited well from the development of light-emitting diodes based on similar technologies, which have entered the market recently. We review here the current status of the field of organic solar cells and discuss different production technologies as well as study the important parameters to improve their performance.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400094498

Organic solar cells: An overview

A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

Conjugated polymers are attractive semiconductors for photovoltaic cells because they are strong absorbers and can be deposited on flexible substrates at low cost. Cells made with a single polymer and two electrodes tend to be inefficient because the photogenerated excitons are usually not split by the built-in electric field, which arises from differences in the electrode work functions. The efficiency can be increased by splitting the excitons at an interface between two semiconductors with offset energy levels. Power conversion efficiencies of almost 4% have been achieved by blending polymers with electron-accepting materials such as C60 derivatives, cadmium selenide, and titanium dioxide. We predict that efficiencies higher than 10% can be achieved by optimizing the cell's architecture to promote efficient exciton splitting and charge transport and by reducing the band gap of the polymer so that a larger fraction of the solar spectrum can be absorbed.

Conjugated Polymer Photovoltaic Cells

Organic light-emitting diodes (OLEDs) show promise for applications as high-quality self-emissive displays for portable devices such as cellular phones and personal organizers. Although monochrome operation is sufficient for some applications, the extension to multi-colour devices--such as RGB (red, green, blue) matrix displays--could greatly enhance their technological impact. Multi-colour OLEDs have been successfully fabricated by vacuum deposition of small electroluminescent molecules, but solution processing of larger molecules (electroluminescent polymers) would result in a cheaper and simpler manufacturing process. However, it has proved difficult to combine the solution processing approach with the high-resolution patterning techniques required to produce a pixelated display. Recent attempts have focused on the modification of standard printing techniques, such as screen printing and ink jetting, but those still have technical drawbacks. Here we report a class of electroluminescent polymers that can be patterned in a way similar to standard photoresist materials--soluble polymers with oxetane sidegroups that can be crosslinked photochemically to produce insoluble polymer networks in desired areas. The resolution of the process is sufficient to fabricate pixelated matrix displays. Consecutive deposition of polymers that are luminescent in each of the three RGB colours yielded a device with efficiencies comparable to state-of-the-art OLEDs and even slightly reduced onset voltages.

Multi-colour organic light-emitting displays by solution processing.

Influence of the anodic work function on the performance of organic solar cells

Continuously variable hole injection in organic light emitting diodes.

PEDOT (Poly(3,4-ethylenedioxythiophene)) layers were prepared by electrochemical polymerization of the respective monomer. Thereafter, these layers were electrochemically adjusted to different equilibrium potentials and they were investigated with Kelvin Probe measurements. A change in work function could be observed yielding a linear correlation with the pre-adjusted electrochemical potential. These PEDOT layers have been utilized in OLEDs in their accessible range of work functions. Internal energy conditions of the OLEDs were characterized in a photovoltaic setup yielding a linear correlation of the open circuit voltage on the pre-adjusted potential. In a second step the efficiency was determined for devices with Ca cathode (space-charge-limited electron current) as well as for devices with Al cathode (injection-limited electron current). These devices could be optimized in efficiency by adjusting the hole current to the electron current, which was determined by the work function of the cathodic metal. The optimum could be explained in zero-order approximation in terms of a balanced bimolecular reaction between holes and electrons.

Optimization of organic semiconductor devices by anode modification

Frictional wear of polymeric materials is usually considered as a process damaging the polymeric material. It is known that friction at polymer surfaces increases the temperature of the polymeric material by several tens of degrees [1]. Tabor published some very fundamental considerations on the molecular and atomic processes in friction and wear [2, 3]. In most of the investigations until now wear is considered as a damaging process but in 1991 Wittmann et al. published a paper [4], in which they describe the formation of thin oriented films by a frictional process. The oriented ultrathin PTFE films resulting from a frictional wear process were used as a substrate for epitaxially orienting low and high moleculer mass linear organic molecules (liquid crystals etc) [5], and also for physical vapor deposited metals [6]. In their method they use a sliding speed of about 1 mm/s. As ultra-thin polymeric films play a major role in many modern technologies (polymeric semiconductors etc.), their preparation is very important. Considering that a relatively low sliding speed was used in the previous work of the frictional transfer processes [7–12], we have designed an experimental setup with about three orders of magnitude higher sliding speed. This may give us the opportunity to vary the experimental parameters like heat production caused by the friction, shear rates and so on over a much larger scale. As shown in Fig. 1, an experimental setup is described, in which shear rates (γ ) of about 108 s−1 in the polymer rods at the interface to the substrate have been performed. The apparatus consists of a piston which is accelerated

Holger Frohne

Papers

Multi-colour organic light-emitting displays by solution processing.

Influence of the anodic work function on the performance of organic solar cells

Continuously variable hole injection in organic light emitting diodes.

Optimization of organic semiconductor devices by anode modification

Friction-transfer of polymeric materials using ultra-high shear rates