L. J. A. Koster

Light intensity dependence of open-circuit voltage of polymer:fullerene solar cells

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.

Ultimate efficiency of polymer/fullerene bulk heterojunction solar cells

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%.

Bimolecular recombination in polymer/fullerene bulk heterojunction solar cells

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.

Origin of the light intensity dependence of the short-circuit current of polymer/fullerene solar cells

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.

Thickness dependence of the efficiency of polymer:fullerene bulk heterojunction solar cells

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 100nm 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.

Effect of metal electrodes on the performance of polymer:fullerene bulk heterojunction solar cells

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-phenylenevinylene) (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.

Massively parallel kinetic Monte Carlo simulations of charge carrier transport in organic semiconductors

A parallel, lattice based Kinetic Monte Carlo simulation is developed that runs on a GPGPU board and includes Coulomb like particle-particle interactions. The performance of this computationally expensive problem is improved by modifying the interaction potential due to nearby particle moves, instead of fully recalculating it. This modification is achieved by adding dipole correction terms that represent the particle move. Exact evaluation of these terms is guaranteed by representing all interactions as 32-bit floating numbers, where only the integers between - 2 22 and 222 are used. We validate our method by modelling the charge transport in disordered organic semiconductors, including Coulomb interactions between charges. Performance is mainly governed by the particle density in the simulation volume, and improves for increasing densities. Our method allows calculations on large volumes including particle-particle interactions, which is important in the field of organic semiconductors.

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.