Silver-Hamill Turren-Cruz

Migration of cations induces reversible performance losses over day/night cycling in perovskite solar cells

Perovskites have been demonstrated in solar cells with a power conversion efficiency of well above 20%, which makes them one of the strongest contenders for next generation photovoltaics. While there are no concerns about their efficiency, very little is known about their stability under illumination and load. Ionic defects and their migration in the perovskite crystal lattice are some of the most alarming sources of degradation, which can potentially prevent the commercialization of perovskite solar cells (PSCs). In this work, we provide direct evidence of electric field-induced ionic defect migration and we isolate their effect on the long-term performance of state-of-the-art devices. Supported by modelling, we demonstrate that ionic defects, migrating on timescales significantly longer (above 103 s) than what has so far been explored (from 10−1 to 102 s), abate the initial efficiency by 10–15% after several hours of operation at the maximum power point. Though these losses are not negligible, we prove that the initial efficiency is fully recovered when leaving the device in the dark for a comparable amount of time. We verified this behaviour over several cycles resembling day/night phases, thus probing the stability of PSCs under native working conditions. This unusual behaviour reveals that research and industrial standards currently in use to assess the performance and the stability of solar cells need to be adjusted for PSCs. Our work paves the way for much needed new testing protocols and figures of merit specifically designed for PSCs.

Identifying and suppressing interfacial recombination to achieve high open-circuit voltage in perovskite solar cells

With close to 100% internal quantum efficiency over the absorption spectrum, photocurrents in perovskite solar cells (PSCs) are at their practical limits. It is therefore imperative to improve open-circuit voltages (VOC) in order to go beyond the current 100 mV loss-in-potential. Identifying and suppressing recombination bottlenecks in the device stack will ultimately drive the voltages up. In this work, we investigate in depth the recombination at the different interfaces in a PSC, including the charge selective contacts and the effect of grain boundaries. We find that the density of grain boundaries and the use of tunneling layers in a highly efficient PSC do not modify the recombination dynamics at 1 sun illumination. Instead, the recombination is strongly dominated by the dopants in the hole transporting material (HTM), spiro-OMeTAD and PTAA. The reduction of doping concentrations for spiro-OMeTAD yielded VOCs as high as 1.23 V in contrast to PTAA, which systematically showed slightly lower voltages. This work shows that a further suppression of non-radiative recombination is possible for an all-low-temperature PSC, to yield a very low loss-in-potential similar to GaAs, and thus paving the way towards higher than 22% efficiencies.

Enhanced charge carrier mobility and lifetime suppress hysteresis and improve efficiency in planar perovskite solar cells

Perovskite solar cells (PSCs) are very promising lab-scale technologies to deliver inexpensive solar electricity. Low-temperature, planar PSCs are of particularly interest for large-scale deployment due to their inherent suitability for flexible substrates and potential for silicon/perovskite tandems. So far, planar PSCs have been prone to large current–voltage hysteresis and low stabilized power output due to a number of issues associated with this kind of device configuration. We find that the suppression of the yellow-phase impurity (∂-FAPbI3) present in formamidium-based perovskites, by RbI addition, contributes to low hysteresis, higher charge carrier mobility, long-lived carrier lifetimes and a champion stabilized power output of 20.3% using SnOx as the electron selective contact. We study the effects of these impurities on the transient behavior that defines hysteresis and its relation to ionic movement. In addition, we find that the formation of a RbPbI3 phase does not significantly affect the charge carrier lifetimes and consequently the performance of the devices. This brings new physical insights onto the role of different impurities in perovskite solar cells, which make these materials so remarkable.

How the Formation of Interfacial Charge Causes Hysteresis in Perovskite Solar Cells

In this study, we discuss the underlying mechanism of the current–voltage hysteresis in a hybrid lead-halide perovskite solar cell. We have developed a method based on Kelvin probe force microscopy that enables mapping charge redistribution in an operating device upon a voltage- or light pulse with sub-millisecond resolution. We observed the formation of a localized interfacial charge at the anode interface, which screened most of the electric field in the cell. The formation of this charge happened within 10 ms after applying a forward voltage to the device. After switching off the forward voltage, however, these interfacial charges were stable for over 500 ms and created a reverse electric field in the cell. This reverse electric field directly explains higher photocurrents during reverse bias scans by electric field-assisted charge carrier extraction. Although we found evidence for the presence of mobile ions in the perovskite layer during the voltage pulse, the corresponding ionic field contributed only less than 10% to the screening. Our observation of a time-dependent ion concentration in the perovskite layer suggests that iodide ions adsorbed and became neutralized at the hole-selective spiro-OMeTAD electrode. We thereby show that instead of the slow migration of mobile ions, the formation and the release of interfacial charges is the dominating factor for current–voltage hysteresis.

Methylammonium-free, high-performance, and stable perovskite solar cells on a planar architecture

Staying in the black phase Hybrid perovskite solar cells often use the more thermally stable formamidinium (FA) cation rather than methylammonium, but its larger size can create lattice distortion that results in an inactive yellow phase. Turren-Cruz et al. show that by using iodide instead of bromide as the anion (to create a redder bandgap) and an optical mix of cesium, rubidium, and FA cations, they can make solar cells with a stabilized efficiency of more than 20%. No heating steps above 100°C were needed to create the preferred black phase. Science, this issue p. 449 Avoidance of bromide anions and methylammonium cations allows optimal tuning of perovskite bandgaps. Currently, perovskite solar cells (PSCs) with high performances greater than 20% contain bromine (Br), causing a suboptimal bandgap, and the thermally unstable methylammonium (MA) molecule. Avoiding Br and especially MA can therefore result in more optimal bandgaps and stable perovskites. We show that inorganic cation tuning, using rubidium and cesium, enables highly crystalline formamidinium-based perovskites without Br or MA. On a conventional, planar device architecture, using polymeric interlayers at the electron- and hole-transporting interface, we demonstrate an efficiency of 20.35% (stabilized), one of the highest for MA-free perovskites, with a drastically improved stability reached without the stabilizing influence of mesoporous interlayers. The perovskite is not heated beyond 100°C. Going MA-free is a new direction for perovskites that are inherently stable and compatible with tandems or flexible substrates, which are the main routes commercializing PSCs.