Krishna Feron

Organic Solar Cells: Understanding the Role of Förster Resonance Energy Transfer

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by Förster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of Förster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.

Exciton transport in organic semiconductors: Förster resonance energy transfer compared with a simple random walk

Forster resonance energy transfer theory (FRET) and a simple random walk (RW) are both implemented in a dynamic Monte Carlo simulation with the aim of determining the exciton diffusion length from photoluminescence (PL) measurements. The calculated diffusion lengths obtained from both models are shown to be the same. As such, given that the computational time of a random walk is typically 2–3 orders of magnitude smaller than the FRET approach, this work shows that the RW methodology can be a preferable model for the determination of diffusion lengths. We also show that the RW approach may also be implemented in Monte Carlo simulations that describe organic solar cells. Despite the fact that (compared with FRET) RW does not account for non-nearest neighbor hopping or energy relaxation, we show that the resulting overestimation of the simulated current will not exceed 2% for typical OPV parameters. In addition, by taking advantage of the gain in speed we are able to investigate the impact of the exciton dif...

Towards the development of a virtual organic solar cell: An experimental and dynamic Monte Carlo study of the role of charge blocking layers and active layer thickness

Monte Carlo (MC) simulations have been used to fully model organic solar cells. The quantum efficiency and short-circuit current of these virtual devices are in excellent agreement with experimental measurements. Simulations show that, contrary to expectation, indium tin oxide/poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)/poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methylester (PCBM)/aluminium devices lack effective charge blocking layers at the electrode interfaces. X-ray photoelectron spectroscopy depth profiling shows that despite a PCBM-rich region near the cathode, interface intermixing at the electrodes combined with incomplete PCBM coverage leads to significant interface recombination. This work highlights the effectiveness of MC simulations as a predictive tool and emphasizes the need to control electrode interface processes.

Comparative degradation and regeneration of polymer solar cells with different cathodes.

A comparative degradation study of solar cells based on a bulk-heterojunction (BHJ) blend of poly(3-hexylethiophene) (P3HT) and phenyl [6,6] C61 butyric acid methyl ester (PCBM) with two different cathodes is reported. Poly(ethylene-dioxythiphene):poly(styrene sulfonate) (PEDOT:PSS) coated ITO electrodes were used as the anode, whereas Ca/Al and Ca/Ag electrodes were used as cathodes. Fully degraded devices were subjected to thermal annealing under inert atmosphere. The performance of degraded solar cells with a Ca/Al cathode exhibited no improvement after treatment. However the solar cells with a Ca/Ag cathode exhibited a considerable recovery in their performance following annealing under a nitrogen atmosphere. Indeed, these solar cells could be subjected to many degradation and regeneration cycles. Current density-voltage (J-V) characteristics and X-ray photoelectron spectroscopy (XPS) studies show that this behavior arises from the complex chemical thermodynamics of the reactions that can occur at the cathode/active layer interface. In particular, the recovery of device performance for solar cells with a Ca/Ag cathode is due to the reversible oxidation of Ag upon thermal annealing.

Enhanced regeneration of degraded polymer solar cells by thermal annealing

The degradation and thermal regeneration of poly(3-hexylethiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and P3HT:indene-C60 bisadduct (ICBA) polymer solar cells, with Ca/Al and Ca/Ag cathodes and indium tin oxide/poly(ethylene-dioxythiophene):polystyrene sulfonate anode have been investigated. Degradation occurs via a combination of three primary pathways: (1) cathodic oxidation, (2) active layer phase segregation, and (3) anodic diffusion. Fully degraded devices were subjected to thermal annealing under inert atmosphere. Degraded solar cells possessing Ca/Ag electrodes were observed to regenerate their performance, whereas solar cells having Ca/Al electrodes exhibited no significant regeneration of device characteristics after thermal annealing. Moreover, the solar cells with a P3HT:ICBA active layer exhibited enhanced regeneration compared to P3HT:PCBM active layer devices as a result of reduced changes to the active layer morphology. Devices combining a Ca/Ag cathode and P3HT:ICBA ...

A low-cost mixed fullerene acceptor blend for printed electronics

The synthesis and performance of a cost-effective mixed fullerene at the 100+ g scale with a reaction yield of 85% is demonstrated. The cost to convert a fullerene such as C60 into the mixed acceptor blend is less than

Solution processable interface materials for nanoparticulate organic photovoltaic devices

1 g−1. The photovoltaic performance of the mixed acceptor is demonstrated in both small scale and roll-to-roll printed devices.

Modelling transport in nanoparticle organic solar cells using Monte Carlo methods

Nanoparticulate zinc oxide can be prepared at low temperatures from solution processable zinc acetylacetonate. The use of this material as a cathode interfacial layer in nanoparticulate organic photovoltaic devices results in comparable performances to those based on reactive calcium layers. Importantly, the enhanced degradation stability and full solution processability make zinc oxide a more desirable material for the fabrication of large area printed devices.

Switched photocurrent on tin sulfide-based nanoplate photoelectrodes

Water-based nanoparticle (NP) organic solar cells eliminate the need for harmful organic solvents during deposition. However, the core-shell NP structure should limit charge extraction resulting in poor performance. Here, we use dynamic Monte Carlo modelling to show that for optimised NP structures the core-shell character does not severely limit performance. Simulations further reveal that small NPs are more susceptible to extensive phase segregation, which diminishes charge carrier percolation pathways from the cores to the electrodes and thus inhibits charge extraction. Simulated performance behaviour was used to propose an explanation for the experimentally observed change in performance due to annealing.

An applied light-beam induced current study of dye-sensitised solar cells: Photocurrent uniformity mapping and true photoactive area evaluation

A new type of SnS2 nanoplate photoelectrode is prepared by using a mild wet-chemical method. Depending on the calcination temperatures, SnS2 -based photoelectrodes can either retain their n-type nature with greatly enhanced anodic photocurrent density (ca. 1.2 mA cm-2 at 0.8 V vs. Ag/AgCl) or be completely converted into p-type SnS to generate approximately 0.26 mA cm-2 cathodic photocurrent density at -0.8 V vs. Ag/AgCl. The dominance of sulfur and tin vacancies are found to account for the dramatically different photoelectrochemical behaviors of n-type SnS2 and p-type SnS photoelectrodes. In addition, the band structures of n-type SnS2 and p-type SnS photoelectrodes are also deduced, which may provide an effective strategy for developing SnS2 /SnS films with controllable energy-band levels through a simple calcination treatment.