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

Converting solar energy into electricity provides a much-needed solution to the energy crisis the world is facing today. Polymer solar cells have shown potential to harness solar energy in a cost-effective way. Significant efforts are underway to improve their efficiency to the level of practical applications. Here, we report highly efficient polymer solar cells based on a bulk heterojunction of polymer poly(3-hexylthiophene) and methanofullerene. Controlling the active layer growth rate results in an increased hole mobility and balanced charge transport. Together with increased absorption in the active layer, this results in much-improved device performance, particularly in external quantum efficiency. The power-conversion efficiency of 4.4% achieved here is the highest published so far for polymer-based solar cells. The solution process involved ensures that the fabrication cost remains low and the processing is simple. The high efficiency achieved in this work brings these devices one step closer to commercialization.

https://yylab.seas.ucla.edu/papers/yy-pv-7-slow growth-nm-05.pdf

High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends

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

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

Tandem solar cells, in which two solar cells with different absorption characteristics are linked to use a wider range of the solar spectrum, were fabricated with each layer processed from solution with the use of bulk heterojunction materials comprising semiconducting polymers and fullerene derivatives. A transparent titanium oxide (TiO x ) layer separates and connects the front cell and the back cell. The TiO x layer serves as an electron transport and collecting layer for the first cell and as a stable foundation that enables the fabrication of the second cell to complete the tandem cell architecture. We use an inverted structure with the low band-gap polymer-fullerene composite as the charge-separating layer in the front cell and the high band-gap polymer composite as that in the back cell. Power-conversion efficiencies of more than 6% were achieved at illuminations of 200 milliwatts per square centimeter.

http://science.sciencemag.org/content/sci/317/5835/222.full.pdf

Efficient tandem polymer solar cells fabricated by all-solution processing.

The dependence of the performance of OC(1)C(10)-PPV:PCBM (poly(2-methoxy-5-(3',7'-dimethyloetyloxy)-p-phenylene vinylene):methanofullerene [6,6]-phenyl C(61)-butyric acid methyl ester)-based bulk heterojunction solar cells on their composition has been investigated. With regard to charge transport, we demonstrate that the electron mobility gradually increases on increasing the PCBM weight ratio, up to 80 wt.-%, and subsequently saturates to its bulk value. Surprisingly, the hole mobility in the PPV phase shows an identical behavior and saturates beyond 67 wt.-% PCBM, a value which is more than two orders of magnitude higher than that of the pure polymer. The experimental electron and hole mobilities were used to study the photocurrent generation of OC(1)C(10)-PPV:PCBM bulk-heterojunction (BHJ) solar cells. From numerical calculations, it is shown that for PCBM concentrations exceeding 80 wt.-% reduced light absorption is responsible for the loss of device performance. From 80 to 67 wt.-%, the decrease in power conversion efficiency is mainly due to a decreased separation efficiency of bound electron-hole (e-h) pairs. Below 67 wt.-%, the performance loss is governed by a combination of a reduced generation rate of e-h pairs and a strong decrease in hole transport.

/pdf/compositional-dependence-of-the-performance-of-poly-p-1k13wt9w9r.pdf

Compositional dependence of the performance of poly(p-phenylene vinylene): Methanofullerene bulk-heterojunction solar cells

A solution-processed polymer tandem cell fabricated by stacking two single cells in series is demonstrated. The two bulk-heterojunction subcells have complementary absorption maxima at lambda(max)similar to 850 nn and lambda(max)similar to 550 nm, respectively. A composite middle electrode is applied that serves both as a charge-recombination center and as a protecting layer for the first cell during spin-coating of the second cell. The subcells are electronically coupled in series, which leads to a high open-circuit voltage of 1.4 V, equal to the sum of each subcell. The layer thickness of the first (bottom) cell is tuned to maximize the optical absorption of the second (top) cell. The performance of the tandem cell is presently limited by the relatively low photocurrent generation in the small-bandgap polymer of the top cell. The combination of our tandem architecture with more efficient small-bandgap materials will enable the realization of highly efficient organic solar cells in the near future.

Solution-processed organic tandem solar cells

Progress in environmental stability and processability, and the increase of the field-effect mobility of organic semiconductors has triggered their use as the active element in microelectronic devices. The advantages of their application are the easy processing, for example, spin-coating and ink-jet printing, without a temperature hierarchy, and their mechanical flexibility. Applications are foreseen in the field of large-area electronics where numerous devices are integrated on low-cost substrates such as plastics. The first flexible, even rollable, quarter video graphics array (QVGA) active matrix displays based on organic semiconductors have already been reported.[1]

/pdf/dynamics-of-threshold-voltage-shifts-in-organic-and-34yqr3q7h1.pdf

de B Bert Boer

Papers

Compositional dependence of the performance of poly(p-phenylene vinylene): Methanofullerene bulk-heterojunction solar cells

Solution-processed organic tandem solar cells

Dynamics of Threshold Voltage Shifts in Organic and Amorphous Silicon Field‐Effect Transistors