Stephan van Reenen

Modeling Anomalous Hysteresis in Perovskite Solar Cells

Organic-inorganic lead halide perovskites are distinct from most other semiconductors because they exhibit characteristics of both electronic and ionic motion. Accurate understanding of the optoelectronic impact of such properties is important to fully optimize devices and be aware of any limitations of perovskite solar cells and broader optoelectronic devices. Here we use a numerical drift-diffusion model to describe device operation of perovskite solar cells. To achieve hysteresis in the modeled current-voltage characteristics, we must include both ion migration and electronic charge traps, serving as recombination centers. Trapped electronic charges recombine with oppositely charged free electronic carriers, of which the density depends on the bias-dependent ion distribution in the perovskite. Our results therefore show that reduction of either the density of mobile ionic species or carrier trapping at the perovskite interface will remove the adverse hysteresis in perovskite solar cells. This gives a clear target for ongoing research effort and unifies previously conflicting experimental observations and theories.

A Unifying Model for the Operation of Light-Emitting Electrochemical Cells

The application of doping in semiconductors plays a major role in the high performances achieved to date in inorganic devices. In contrast, doping has yet to make such an impact in organic electronics. One organic device that does make extensive use of doping is the light-emitting electrochemical cell (LEC), where the presence of mobile ions enables dynamic doping, which enhances carrier injection and facilitates relatively large current densities. The mechanism and effects of doping in LECs are, however, still far from being fully understood, as evidenced by the existence of two competing models that seem physically distinct: the electrochemical doping model and the electrodynamic model. Both models are supported by experimental data and numerical modeling. Here, we show that these models are essentially limits of one master model, separated by different rates of carrier injection. For ohmic nonlimited injection, a dynamic p-n junction is formed, which is absent in injection-limited devices. This unification is demonstrated by both numerical calculations and measured surface potentials as well as light emission and doping profiles in operational devices. An analytical analysis yields an upper limit for the ratio of drift and diffusion currents, having major consequences on the maximum current density through this type of device.

Universal Transients in Polymer and Ionic Transition Metal Complex Light-Emitting Electrochemical Cells

Two types of light-emitting electrochemical cells (LECs) are commonly distinguished, the polymer-based LEC (p-LEC) and the ionic transition metal complex-based LEC (iTMC-LEC). Apart from marked differences in the active layer constituents, these LEC types typically show operational time scales that can differ by many orders of magnitude at room temperature. Here, we demonstrate that despite these differences p-LECs and iTMC-LECs show current, light output, and efficacy transients that follow a universal shape. Moreover, we conclude that the turn-on time of both LEC types is dominated by the ion conductivity because the turn-on time exhibits the same activation energy as the ion conductivity in the off-state. These results demonstrate that both types of LECs are really two extremes of one class of electroluminescent devices. They also implicate that no fundamental difference exists between charge transport in small molecular weight or polymeric mixed ionic and electronic conductive materials. Additionally, it follows that the ionic conductivity is responsible for the dynamic properties of devices and systems using them. This likely extends to mixed ionic and electronic conductive materials used in organic solar cells and in a variety of biological systems.

Interface-Dependent Ion Migration/Accumulation Controls Hysteresis in MAPbI3 Solar Cells

Hysteresis in the current-voltage characteristics of hybrid organic-inorganic perovskite-based solar cells is one of the fundamental aspects of these cells that we do not understand well. One possible cause, suggested for the hysteresis, is polarization of the perovskite layer under applied voltage and illumination bias, due to ion migration within the perovskite. To study this problem systemically current-voltage characteristics of both regular (light incident through the electron conducting contact) and so-called inverted (light incident through the hole conducting contact) perovskite cells were studied at different temperatures and scan rates. We explain our results by assuming that the effects of scan rate and temperature on hysteresis are strongly correlated to ion migration within the device, with the rate-determining step being ion migration at/across the interfaces of the perovskite layer with the contact materials. By correlating between the scan rate with the measurement temperature we show that the inverted and regular cells operate in different hysteresis regimes, with different activation energies of 0.28+-0.04 eV and 0.59+-0.09 eV, respectively. We suggest that the differences, observed between the two architectures are due to different rates of ion migration close to the interfaces, and conclude that the diffusion coefficient of migrating ions in the inverted cells is 3 orders of magnitude higher than in the regular cells, leading to different accumulation rates of ions near the interfaces. Analysis of VOC as a function of temperature shows that the main recombination mechanism is trap-assisted (Shockley-Read Hall, SRH) in the space charge region, similar to what is the case for other thin film inorganic solar cells.

Design rules for light-emitting electrochemical cells delivering bright luminance at 27.5 percent external quantum efficiency

The light-emitting electrochemical cell promises cost-efficient, large-area emissive applications, as its characteristic in-situ doping enables use of air-stabile electrodes and a solution-processed single-layer active material. However, mutual exclusion of high efficiency and high brightness has proven a seemingly fundamental problem. Here we present a generic approach that overcomes this critical issue, and report on devices equipped with air-stabile electrodes and outcoupling structure that deliver a record-high efficiency of 99.2 cd A−1 at a bright luminance of 1910 cd m−2. This device significantly outperforms the corresponding optimized organic light-emitting diode despite the latter employing calcium as the cathode. The key to this achievement is the design of the host–guest active material, in which tailored traps suppress exciton diffusion and quenching in the central recombination zone, allowing efficient triplet emission. Simultaneously, the traps do not significantly hamper electron and hole transport, as essentially all traps in the transport regions are filled by doping.Cost-efficient light-emitting electrochemical cells can deliver unique functions, but suffer because strong brightness has only been obtained at modest efficiency. Tang et al. report on rationally designed devices that are both bright and efficient, thus representing a major step towards commercialization.