Organic solar cells
Organic solar cells differ from conventional inorganic ones not only in their flexibility, but also in their fundamental physics. Organic materials are disordered, meaning that charges tend to be localised and move by hopping, unlike the band transport in inorganic devices. In addition, the localisation of the electron and the hole increases their Coulomb attraction, making it harder to separate them and produce an electric current.
It is still unclear exactly how the charges overcome their considerable electrostatic attraction, sometimes with an efficiency approaching 100%, although we have shown that entropy and disorder play a critical role. We are working to understand the fundamental photophysics involved, often in close collaboration with experimentalists, in order to facilitate the rational design of better materials.
- Intercalated vs nonintercalated morphologies in donor−acceptor bulk heterojunction solar cells: PBTTT:fullerene charge generation and recombination revisitedIn this Letter, we study the role of the donor:acceptor interface nanostructure upon charge separation and recombination in organic photovoltaic devices and blend films, using mixtures of PBTTT and two different fullerene derivatives (PC70BM and ICTA) as models for intercalated and nonintercalated morphologies, respectively. Thermodynamic simulations show that while the completely intercalated system exhibits a large free-energy barrier for charge separation, this barrier is significantly lower in the nonintercalated system and almost vanishes when energetic disorder is included in the model. Despite these differences, both femtosecond-resolved transient absorption spectroscopy (TAS) and time-delayed collection field (TDCF) exhibit extensive first-order losses in both systems, suggesting that geminate pairs are the primary product of photoexcitation. In contrast, the system that comprises a combination of fully intercalated polymer:fullerene areas and fullerene-aggregated domains (1:4 PBTTT:PC70BM) is the only one that shows slow, second-order recombination of free charges, resulting in devices with an overall higher short-circuit current and fill factor. This study therefore provides a novel consideration of the role of the interfacial nanostructure and the nature of bound charges and their impact upon charge generation and recombination.
- Electric field and mobility dependent first-order recombination losses in organic solar cellsThe origin of photocurrent losses in the power-generating regime of organic solar cells (OSCs) remains a controversial topic, although recent literature suggests that the competition between bimolecular recombination and charge extraction determines the bias dependence of the photocurrent. Here the steady-state recombination dynamics is studied in bulk-heterojunction OSCs with different hole mobilities from short-circuit to maximum power point. It is shown that in this regime, in contrast to previous transient extracted charge and absorption spectroscopy studies, first-order recombination outweighs bimolecular recombination of photogenerated charge carriers. This study demonstrates that the first-order losses increase with decreasing slower carrier mobility, and attributes them to either mobilization of charges trapped at the donor:acceptor interface through the Poole–Frenkel effect, and/or recombination of photogenerated and injected charges. The dependence of both first-order and higher-order losses on the slower carrier mobility explains why the field dependence of OSC efficiencies has historically been attributed to charge-extraction losses.
- Entropy and disorder enable charge separation in organic solar cellsAlthough organic heterojunctions can separate charges with near-unity efficiency and on a sub-picosecond timescale, the full details of the charge-separation process remain unclear. In typical models, the Coulomb binding between the electron and the hole can exceed the thermal energy kT by an order of magnitude, making it impossible for the charges to separate before recombining. Here, we consider the entropic contribution to charge separation in the presence of disorder and find that even modest amounts of disorder have a decisive effect, reducing the charge-separation barrier to about kT or eliminating it altogether. Therefore, the charges are usually not thermodynamically bound at all and could separate spontaneously if the kinetics otherwise allowed it. Our conclusion holds despite the worst-case assumption of localised, thermalised carriers, and is only strengthened if mechanisms like delocalisation or 'hot' states are also present.
- Slower carriers limit charge generation in organic semiconductor light-harvesting systemsBlends of electron-donating and -accepting organic semiconductors are widely used as photoactive materials in next-generation solar cells and photodetectors. The yield of free charges in these systems is often determined by the separation of interfacial electron–hole pairs, which is expected to depend on the ability of the faster carrier to escape the Coulomb potential. Here we show, by measuring geminate and non-geminate losses and key transport parameters in a series of bulk-heterojunction solar cells, that the charge-generation yield increases with increasing slower carrier mobility. This is in direct contrast with the well-established Braun model where the dissociation rate is proportional to the mobility sum, and recent models that underscore the importance of fullerene aggregation for coherent electron propagation. The behaviour is attributed to the restriction of opposite charges to different phases, and to an entropic contribution that favours the joint separation of both charge carriers.
- Spectral dependence of the internal quantum efficiency of organic solar cells: Effect of charge generation pathwaysThe conventional picture of photocurrent generation in organic solar cells involves photoexcitation of the electron donor, followed by electron transfer to the acceptor via an interfacial charge-transfer state (Channel I). It has been shown that the mirror-image process of acceptor photoexcitation leading to hole transfer to the donor is also an efficient means to generate photocurrent (Channel II). The donor and acceptor components may have overlapping or distinct absorption characteristics. Hence, different excitation wavelengths may preferentially activate one channel or the other, or indeed both. As such, the internal quantum efficiency (IQE) of the solar cell may likewise depend on the excitation wavelength. We show that several model high-efficiency organic solar cell blends, notably PCDTBT:PC70BM and PCPDTBT:PC60/70BM, exhibit flat IQEs across the visible spectrum, suggesting that charge generation is occurring either via a dominant single channel or via both channels but with comparable efficiencies. In contrast, blends of the narrow optical gap copolymer DPP-DTT with PC70BM show two distinct spectrally flat regions in their IQEs, consistent with the two channels operating at different efficiencies. The observed energy dependence of the IQE can be successfully modeled as two parallel photodiodes, each with its own energetics and exciton dynamics but both having the same extraction efficiency. Hence, an excitation-energy dependence of the IQE in this case can be explained as the interplay between two photocurrent-generating channels, without recourse to hot excitons or other exotic processes.