A method for identifying the cause of inefficient salt-doping in organic semiconductors.

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.

Charge carrier thermalization in organic diodes.

Charge carrier mobilities of organic semiconductors are often characterized using steady-state measurements of space charge limited diodes. These measurements assume that charge carriers are in a steady-state equilibrium. In reality, however, energetically hot carriers are introduces by photo-excitation and injection into highly energetic sites from the electrodes. These carriers perturb the equilibrium density of occupied states, and therefore change the overall charge transport properties. In this paper, we look into the effect of energetically hot carriers on the charge transport in organic semiconductors using steady state kinetic Monte Carlo simulations. For injected hot carriers in a typical organic semiconductor, rapid energetic relaxation occurs in the order of tens of nanoseconds, which is much faster than the typical transit time of a charge carrier throught the device. Furthermore, we investigate the impact of photo-generated carriers on the steady-state mobility. For a typical organic voltaic material, an increase in mobility of a factor of 1.1 is found. Therefore, we conclude that the impact of energetically hot carriers on normal device operation is limited.

Controlling the assembly of CdS nanorods via solvent and acidity.

We report control over the phase behavior of CdS nanorods via the solvent and acidity. CdS nanorods were synthesized using alkane phosphonic acid ligands, which were replaced after synthesis by a series of aromatic ligands. Change of ligand enabled us to cast films from different solvents. By replacing toluene with ethanol or water the rod-rod interactions dominate over rod-substrate interactions, thereby favoring simple hexagonal ordering (2D). When dispersed in water, a net electrostatic charge on the nanorods could be induced by deprotonating the ligands at high pH. This net charge favors 2D nematic ordering over homeotropic ordering of the nanorods on a substrate. A calculation of the van der Waals and electrostatic interactions is presented that explains the observed influence of solvent and pH.

Describing the light intensity dependence of polymer:fullerene solar cells using an adapted Shockley diode model.

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.

Scaling theory for percolative charge transport in disordered molecular semiconductors.

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.

Validity of the Einstein relation in disordered organic semiconductors.

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.

Trap-assisted recombination in disordered organic semiconductors.

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 µ(p). 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)µ(p). 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.

Photocurrent generation in polymer-fullerene bulk heterojunctions.

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.