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Doping to enhance the electrical conductivity of organic semiconductors is not without its challenges: The efficacy of this process depends on many factors and it is not always clear how to remedy poor doping. In the case of doping with salts, one of the possible causes of poor doping is a limited yield of integer charge transfer resulting in the presence of both cations and anions in the film. The charge of such ions can severely limit the electrical conductivity, but their presence is not easily determined. Here we introduce a set of simple conductivity measurements to determine whether poor doping in the case where the dopant is a salt is due to limited integer charge transfer. By tracking how the conductivity changes over time when applying a bias voltage for an extended amount of time we can pinpoint whether unwanted ions are present in the film. Firstly, we introduce the principle of this approach by performing numerical simulations that include the movement of ions. We show that the conductivity can increase or decrease depending on the type of ions present in the film. Next, we show that the movement of these dopant ions causes a build-up of space-charge, which makes the current–voltage characteristic non-linear. Next, we illustrate how this approach may be used in practice by doping a fullerene derivative with a series of organic salts. We thus provide a tool to make the optimization of doping more rational. [ABSTRACT FROM AUTHOR]

We use a Monte Carlo model to predict the effect of composition, domain size, and energetic disorder upon the mobility of carriers in an organic donor-acceptor blend. These simulations show that, for the changes in local morphology expected within the thickness of a typical bulk heterojunction photovoltaic device, changes in mobility of more than an order of magnitude are expected. The impact of nonuniform mobility upon space-charge-limited diode and photovoltaic (PV) device performance is examined using a drift-diffusion model. The current passing through a space-charge-limited diode is shown to depend upon the position of the layers with differing mobility. Accurate modeling of the current in such devices can only be achieved using a drift-diffusion model incorporating nonuniform mobility. Inserting a 20 nm thick layer in which the mobility is less by one order of magnitude than in the rest of the 70 nm thick PV device reduced the device efficiency by more than 20%. Therefore it seems vital to exert a high degree of control over the morphology throughout the entire blend PV device, otherwise potential PV performance may be lost. [ABSTRACT FROM AUTHOR]

We studied three n-type polymers of the naphthalenediimide-bithiophene family as electron extraction layers (EELs) in hybrid perovskite solar cells. The recombination mechanism in these devices is found to be heavily influenced by the EEL transport properties. The maximum efficiency of the devices using the n-type polymers EELs did not exceed substantially that of the devices using PC60BM (about 11%), while a substantial improvement in their ambient stability (87% of the initial value after 270 minutes) compared to that using PC60BM (3.5% of the initial value after 270 minutes) was detected. [ABSTRACT FROM AUTHOR]

Solar cells are generally optimised for operation under AM1.5 100 mW cm−2 conditions. This is also typically done for polymer solar cells. However, one of the entry markets for this emerging technology is portable electronics. For this market, the spectral shape and intensity of typical illumination conditions deviate considerably from the standard test conditions (AM1.5, 100 mW cm−2, at 25 °C). The performance of polymer solar cells is strongly dependent on the intensity and spectral shape of the light source. For this reason the cells should be optimised for the specific application. Here a theoretical model is presented that describes the light intensity dependence of P3HT:[C60]PCBM solar cells. It is based on the Shockley diode equation, combined with a metal–insulator–metal model. In this way the observed light intensity dependence of P3HT:[C60]PCBM solar cells can be described using a 1-diode model, allowing fast optimization of polymer solar cells and module design. [ABSTRACT FROM AUTHOR]

The performance of polymer solar cells critically depends on the morphology of the interface between the donor- and acceptor materials that are used to create and transport charge carriers. Solar cells based on poly(3-hexylthiophene) and ZnO were fully characterized in terms of their efficiency and three-dimensional (3D) morphology on the nanoscale. Here, we establish a quantitative link between efficiency and morphology by using the experimental 3D morphology as direct input for a 3D optoelectronic device model. This model includes the effects of exciton diffusion and quenching; space-charge; recombination, generation, drift and diffusion of charge carriers; and the injection/extraction of carriers at the contacts. The observed trend in internal quantum efficiency as a function of layer thickness is reproduced with a single set of parameters. Several morphological aspects that determine the internal quantum efficiency are discussed and compared to other organic solar cells. This first direct use of morphological data in an optoelectronic device model highlights the importance of morphology in solar cells. [ABSTRACT FROM AUTHOR]

The trap-assisted recombination of electrons and holes in organic semiconductors is investigated. The extracted capture coefficients of the trap-assisted recombination process are thermally activated with an identical activation energy as measured for the hole mobility μp. We demonstrate that the rate limiting step for this mechanism is the diffusion of free holes towards trapped electrons in their mutual Coulomb field, with the capture coefficient given by (q/ε)μp. As a result, both the bimolecular and trap-assisted recombination processes in organic semiconductors are governed by the charge carrier mobilities, allowing predictive modeling of organic light-emitting diodes. [ABSTRACT FROM AUTHOR]

We present a scaling theory for charge transport in disordered molecular semiconductors that extends percolation theory by including bonds with conductances close to the percolating one in the random-resistor network representing charge hopping. A general and compact expression is given for the charge mobility for Miller-Abrahams and Marcus hopping on different lattices with Gaussian energy disorder, with parameters determined from numerically exact results. The charge-concentration dependence is universal. The model-specific temperature dependence can be used to distinguish between the hopping models. [ABSTRACT FROM AUTHOR]

it is controversial whether energetic disorder in semiconductors is already sufficient to violate the classical Einstein relation, even in the case of thermal equilibrium. We demonstrate that the Einstein relation is violated only under nonequilibrium conditions due to deeply trapped carriers, as in diffusion- driven current measurements on organic single-carrier diodes. Removal of these deeply trapped carriers by recombination unambiguously proves the validity of the Einstein relation in disordered semiconductors in thermal (quasi)equilibrium. [ABSTRACT FROM AUTHOR]

In organic semiconductors the recombination mechanism is of the Langevin type, controlled by the mobility of the charge carriers. As a result, in organic solar cells the mobility simultaneously controls both the carrier extraction and the losses via carrier recombination. The authors demonstrate that the balance between carrier losses by extraction and by recombination leads to a distinct optimum in the carrier mobility with regard to the efficiency of organic solar cells. For low mobilities recombination losses limit the performance, whereas the efficient extraction at high mobilities leads to a reduction of the open-circuit voltage. [ABSTRACT FROM AUTHOR]

We study the thickness dependence of the performance of bulk heterojunction solar cells based on poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] as electron donor and [6,6]-phenyl C61 butyric acid methyl ester as electron acceptor. Typically, these devices have an active layer thickness of 100 nm at which only 60% of the incoming light is absorbed. Increasing device thickness results in a lower overall power conversion efficiency, mainly due to a lowering of the fill factor. We demonstrate that the decrease in fill factor and hence device efficiency is due to a combination of charge recombination and space-charge effects. [ABSTRACT FROM AUTHOR]

We present model calculations to explore the potential of polymer/fullerene bulk heterojunction solar cells. As a starting point, devices based on poly(3-hexylthiophene) and 6,6-phenyl C61-butyric acid methyl ester (PCBM), reaching 3.5% efficiency, are modeled. Lowering the polymeric band gap will lead to a device efficiency exceeding 6%. Tuning the electronic levels of PCBM in such a way that less energy is lost in the electron transfer process enhances the efficiency to values in excess of 8%. Ultimately, with an optimized level tuning, band gap, and balanced mobilities polymeric solar cells can reach power conversion efficiencies approaching 11%. [ABSTRACT FROM AUTHOR]

Bimolecular recombination in organic semiconductors is known to follow the Langevin expression, i.e., the rate of recombination depends on the sum of the mobilities of both carriers. We show that this does not hold for polymer/fullerene bulk heterojunction solar cells. The voltage dependence of the photocurrent reveals that the recombination rate in these blends is determined by the slowest charge carrier only, as a consequence of the confinement of both types of carriers to two different phases. [ABSTRACT FROM AUTHOR]

A typical feature of polymer/fullerene based solar cells is that the current density under short-circuit conditions (Jsc) does not scale exactly linearly with light intensity (I). Instead, a power law relationship is found given by Jsc∝Iα, where α ranges from 0.85 to 1. In a number of reports this deviation from unity is speculated to arise from the occurrence of bimolecular recombination. We demonstrate that the dependence of the photocurrent in bulk heterojunction solar cells is governed by the build-up of space-charge in the device as a consequence of a difference in electron- and hole mobility. We have verified this for an experimental model system in which the mobility difference can be tuned from one to three orders of magnitude by changing the annealing treatment. [ABSTRACT FROM AUTHOR]

The open-circuit voltage Voc of polymer:fullerene bulk heterojunction solar cells is investigated as a function of light intensity for different temperatures. Devices consisted of a blend of a poly(p-phenylene vinylene) derivative as the hole conductor and 6,6-phenyl C61-butyric acid methyl ester as the electron conductor. The observed photogenerated current and Voc are at variance with classical p–n junction-based models. The influence of light intensity and recombination strength on Voc is consistently explained by a model based on the notion that the quasi-Fermi levels are constant throughout the device, including both drift and diffusion of charge carriers. [ABSTRACT FROM AUTHOR]

An increase in the workfunction of the metal top electrode leads to a reduction of the open-circuit voltage, short-circuit current, and power conversion efficiency of organic bulk-heterojunction solar cells. It has been demonstrated that the photocurrent obtained from an active layer comprised of a blend of poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-p-phenylene vinylene) (OC1C10-PPV) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM), with lithium fluoride topped aluminum, silver, gold, or palladium electrodes, shows a universal behavior when scaled against the effective voltage across the device. Indeed, model calculations confirm that the dependence of the photocurrent on the effective voltage is responsible for the observed variation in performance of each different electrode. Consequently, for any given metal, only the device’s open-circuit voltage is required in order to be able to predict the remaining solar cell parameters. [ABSTRACT FROM AUTHOR]

The current density-voltage (J-V) characteristics of hole-only diodes based on poly(2-methoxy, 5-(2' ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) were measured at a wide temperature and field range. At high electric fields the temperature dependence of the transport vanishes, and all J-V sweeps converge to a power law. Nuclear tunneling theory predicts a power law at high fields that scales with the Kondo parameter. To model the J-V characteristics we have performed master-equation calculations to determine the dependence of charge carrier mobility on electric field, charge carrier density, temperature, and Kondo parameter, using nuclear tunneling transfer rates. We demonstrate that nuclear tunneling, unlike other semiclassical models, provides a consistent description of the charge transport for a large bias, temperature, and carrier density range. [ABSTRACT FROM AUTHOR]

The photocurrent in conjugated polymer-fullerene blends is dominated by the dissociation efficiency of bound electron-hole pairs at the donor-acceptor interface. A model based on Onsager's theory of geminate charge recombination explains the observed field and temperature dependence of the photocurrent in PPV:PCBM blends. At room temperature only 60% of the generated bound electron-hole pairs are dissociated and contribute to the short-circuit current, which is a major loss mechanism in photovoltaic devices based on this material system.