Understanding the Thickness-Dependent Performance of Organic Bulk Heterojunction Solar Cells: The Influence of Mobility, Lifetime, and Space Charge

We investigate the reasons for the dependence of photovoltaic performance on the absorber thickness of organic solar cells using experiments and drift-diffusion simulations. The main trend in photocurrent and fill factor versus thickness is determined by mobility and lifetime of the charge carriers. In addition, space charge becomes more and more important the thicker the device is because it creates field free regions with low collection efficiency. The two main sources of space-charge effects are doping and asymmetric mobilities. We show that for our experimental results on Si-PCPDTBT:PC₇₁BM (poly­[(4,40-bis­(2-ethylhexyl)­dithieno­[3,2-<i>b</i>:20,30-<i>d</i>]­silole)-2,6-diyl-<i>alt</i>-(4,7-bis­(2-thienyl)-2,1,3-benzothiadiazole)-5,50-diyl]:[6,6]-phenyl C71-butyric acid methyl ester) solar cells, the influence of doping is most likely the dominant influence on the space charge and has an important effect on the thickness dependence of performance

Understanding the Thickness-Dependent Performance of Organic Bulk Heterojunction Solar Cells: The Influence of Mobility, Lifetime, and Space Charge

We investigate the reasons for the dependence of photovoltaic performance on the absorber thickness of organic solar cells using experiments and drift-diffusion simulations. The main trend in photocurrent and fill factor versus thickness is determined by mobility and lifetime of the charge carriers. In addition, space charge becomes more and more important the thicker the device is because it creates field free regions with low collection efficiency. The two main sources of space-charge effects are doping and asymmetric mobilities. We show that for our experimental results on Si-PCPDTBT:PC₇₁BM (poly­[(4,40-bis­(2-ethylhexyl)­dithieno­[3,2-<i>b</i>:20,30-<i>d</i>]­silole)-2,6-diyl-<i>alt</i>-(4,7-bis­(2-thienyl)-2,1,3-benzothiadiazole)-5,50-diyl]:[6,6]-phenyl C71-butyric acid methyl ester) solar cells, the influence of doping is most likely the dominant influence on the space charge and has an important effect on the thickness dependence of performance

Sensitivity of the Mott–Schottky Analysis in Organic Solar Cells

The application of Mott–Schottky analysis to capacitance–voltage measurements of polymer:fullerene solar cells is a frequently used method to determine doping densities and built-in voltages, which have important implications for understanding the device physics of these cells. Here we compare drift-diffusion simulations with experiments to explore the influence and the detection limit of doping in situations where device thickness and doping density are too low for the depletion approximation to be valid. The results of our simulations suggest that the typically measured values on the order of 5 × 10¹⁶ cm^–3 for doping density in thin films of 100 nm or lower may not be reliably determined from capacitance measurements and could originate from a completely intrinsic active layer. In addition, we explain how the violation of the depletion approximation leads to a strong underestimation of the actual built-in voltage by the built-in voltage <i>V</i>_MS determined by Mott–Schottky analysis

Dependence of Charge Separation Efficiency on Film Microstructure in Poly(3-hexylthiophene-2,5-diyl):[6,6]-Phenyl-C₆₁ Butyric Acid Methyl Ester Blend Films

Herein we address the factors controlling photocurrent generation in P3HT:PCBM blend films as a function of blend composition and annealing treatment. Absorption, photoluminescence, and transient absorption spectroscopy are used to distinguish the role of exciton dissociation, charge pair separation, and charge collection. Variations in blend film microstructure with composition and annealing treatment are studied using X-ray diffraction. While the trend in photocurrent generation with composition and annealing [Muller, et al., <i>Adv. Mater.</i> <b>2008</b>, <i>20</i>, 3510] does not follow the trend in exciton dissociation, it closely follows the trend in charge pair generation. Moreover, charge pair generation efficiency is positively correlated to the degree of polymer crystallization and the appearance of large domains of both polymer and fullerene phases. We argue that larger domains assist charge pair separation by increasing the probability of escape from the P3HT:PCBM interface, thus reducing geminate charge recombination