Application of an Electro-Optical Model for Organic Solar Cells Based on the Principle of Detailed Balance

Marcos Soldera1, Kurt Taretto1 and Thomas Kirchartz2

1

Deparamento de Electrotecnia, Universidad Nacional del Comahue-CONICET, Buenos Aires 1400, Neuquen (8300), Argentina 2 IEF5-Photovoltaik, Forschungszentrum Jlich, 52425 Jlich, Germany e-mail: msoldera@gmail.com

1. Abstract
We apply a recently developed electro-optical model [1] to experimental data of organic solar cells prepared by different research groups. The active layers of these cells consist of a blend between two organic materials, namely a conduction electron donor and an acceptor, which effectively form a bulk heterojunction (BHJ) homogeneously distributed in the whole active layer, where dissociation of the photogenerated excitons and charge transfer take place. Fig 1 shows a schematic two dimensional band diagram depicting the absorption, exciton diffusion and dissociation and free carriers transport to the contacts. After fitting current-voltage (J-V) curves in the dark and under illumination and external quantum efficiency (EQE) data, we extracted important device parameters such as exciton diffusion length L, bound pair lifetime kf-1 and exciton collection efficiency fc. Fig. 2 shows the fit of a J-V measurement on a cell composed of a mixture between poly [9,9didecanefluorenealt-(bis-thienylene)benzothidiazole] (PF10TBT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) (1:4 in weight) prepared by Ref. [2]. Several blend materials were studied and, particularly, we obtained from simulating poly-3-hexylthiophene (P3HT):PCBM (1:1 in weight) cells an L = 5-12 nm in the donor phase and L = 5.3 nm in the acceptor phase, which is close to the value of 5 nm measured by Ref. [3] with time-resolved emission techniques. The bound pair lifetime kf-1 varied between 1-10 s, which is lower than the 50 s obtained by Ref. [4] using a simpler model. The exciton collection efficiency fc allows us to quantify the photocurrent loss caused by incomplete exciton harvesting in the blend from J-V fits, and in the donor and acceptor materials from an EQE measurement. The simulated cells yield values of fc in the range 80-91%. Including optical interference effects and field-dependent bound pair dissociation, data with varying blend thickness are also well reproduced by the model. For specific conditions, we show that the short circuit current and the thickness dependence are predicted by a simple analytical expression that contains exciton dynamics as well as optics. Experimental data of the P3HT:PCBM blend reported by Ref. [5] and the fits with the numerical and the analytical approach are shown in Fig. 3. The good agreement obtained with the analytical expressions suggests that they could be utilized as simple tools to estimate the blend thickness at which the photocurrent is maximized.

2. References
[1] T. Kirchartz, B.E. Pieters, K. Taretto, and U. Rau, Electro-Optical Modeling of Bulk Heterojunction Solar Cells, Journal of Applied Physics 104, 2008, 094513-19. [2] D. Veldman, O. Ipek, S.C.J. Meskers, J. Sweelssen, M.M. Koetse, S.C. Veenstra, J.M. Kroon, S.S. Bavel, J. Loos, and R.A.J. Janssen, Compositional and Electric Field Dependence of the Dissociation of Charge Transfer Excitons in Alternating Polyfluorene Copolymer/Fullerene Blends, Journal of the American Chemical Society 130, 2008, 77217735. [3] S. Cook, A. Furube, R. Katoh, and L. Han, Estimate of Singlet Diffusion Lengths in PCBM Films by TimeResolved Emission Studies, Chemical Physics Letters 478, 2009, 3336. [4] V.D. Mihailetchi, H.X. Xie, B. de Boer, L.J.A. Koster, and P.W.M. Blom, Charge Transport and Photocurrent Generation in Poly(3-hexylthiophene): Methanofullerene Bulk-Heterojunction Solar Cells, Advanced Functional Materials 16, 2006, 699708. [5] F. Monestier, J. Simon, P. Torchio, L. Escoubas, F. Flory, S. Bailly, R. Bettignies, S. Guillerez, and C. Defranoux, Modeling the Short-Circuit Current Density of Polymer Solar Cells Based on P3HT:PCBM Blend, Solar Energy Materials and Solar Cells 91, 2007, 405 410.

Fig. 1: Two dimensional energy band diagram used to model BHJ cells. Free carriers are generated at each point along the x-axis after a photogenerated exciton diffuses along the y-direction and dissociates at the donor-acceptor interface. Fig. 2: a) Experimental J-V curve under filtered white light illumination from Ref. [2] (open circles) and the fit with the model (solid line), and b) the corresponding dark curve.

Fig. 3: Experimental short circuit current density JSC as a function of blend thickness obtained by Ref. [5] (open circles), the fit with the model (solid line) and JSC calculated with the analytical approach (dashed line). The inset shows a simulated J-V curve at a blend thickness of 136 nm.