Advancing inverted (p–i–n) perovskite solar cells (PSCs) is key to further enhance the power conversion efficiency (PCE) and stability of flexible and perovskite-based tandem photovoltaics. Yet, the presence of defects at grain boundaries and in particular interfacial recombination at the perovskite/electron transporting layer interface induce severe non-radiative recombination losses, limiting the open-circuit voltage (VOC) and fill factor (FF) of PSCs in this architecture. In this work, we introduce a dual passivation strategy using the long chain alkylammonium salt phenethylammonium chloride (PEACl) both as an additive and for surface treatment to simultaneously passivate the grain boundaries and the perovskite/C60 interface. Using [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) as a hole transporting layer and a methylammonium (MA)-free Cs0.18FA0.82PbI3 perovskite absorber with a bandgap of ∼1.57 eV, prolonged charge carrier lifetime and an on average 63 meV enhanced internal quasi-Fermi level splitting are achieved upon dual passivation compared to reference p–i–n PSCs. Thereby, we achieve one of the highest PCEs for p–i–n PSCs of 22.7% (stabilized at 22.3%) by advancing simultaneously the VOC and FF up to 1.162 V and 83.2%, respectively. Using a variety of experimental techniques, we attribute the positive effects to the formation of a heterogeneous 2D Ruddlesden–Popper (PEA)2(Cs1−xFAx)n−1Pbn(I1−yCly)3n+1 phase at the grain boundaries and surface of the perovskite films. At the same time, the activation energy for ion migration is significantly increased, resulting in enhanced stability of the PSCs under light, humidity, and thermal stress. The presented dual passivation strategy highlights the importance of defect management both in the grain boundaries and the surface of the perovskite absorber layer using a proper passivation material to achieve both highly efficient and stable inverted p–i–n PSCs.

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Two birds with one stone: dual grain-boundary and interface passivation enables >22% efficient inverted methylammonium-free perovskite solar cells

Apparent Defect Densities in Halide Perovskite Thin Films and Single Crystals

In recent years, perovskite light-emitting diodes (PeLEDs) have emerged as a promising new lighting technology with high external quantum efficiency, color purity, and wavelength tunability, as well as, low-temperature processability. However, the operational stability of PeLEDs is still insufficient for their commercialization. The generation and migration of ionic species in metal halide perovskites has been widely acknowledged as the primary factor causing the performance degradation of PeLEDs. Herein, this topic is systematically discussed by considering the fundamental and engineering aspects of ion-related issues in PeLEDs, including the material and processing origins of ion generation, the mechanisms driving ion migration, characterization approaches for probing ion distributions, the effects of ion migration on device performance and stability, and strategies for ion management in PeLEDs. Finally, perspectives on remaining challenges and future opportunities are highlighted. 

Ion Migration in Perovskite Light‐Emitting Diodes: Mechanism, Characterizations, and Material and Device Engineering

Organic-inorganic hybrid perovskite (OIHPs) solar cells are the most promising alternatives to traditional silicon solar cells, with a certified power conversion efficiency beyond 25%. However, the poor stability of OHIPs is one of the thorniest obstacles that hinder its commercial development. Among all the factors affecting stability, ion migration is prominent because it is unavoidable and intrinsic in OHIPs. Therefore, it is important to understand the mechanism for ion migration and regulation strategies. Herein, the types of ions that may migrate in OHIPs are first discussed; afterward, the migrating channels are demonstrated. The effects of ion migration are further elaborated. While ion migration can facilitate the p-i-n structure in some cases, the current hysteresis and other adverse effects such as phase segregation in OHIPs attract widespread attention. Based on these, several recent strategies to suppress the ion migration are enumerated, including the introduction of alkali cations, organic additives, grain boundaries passivation, and employment of low-dimensional perovskites. Finally, the prospect for further modulating the ion migration and more stable perovskite solar cells is proposed. 

Ion Migration in Organic–Inorganic Hybrid Perovskite Solar Cells: Current Understanding and Perspectives

Perovskite semiconductors differ from most inorganic and organic semiconductors due to the presence of mobile ions in the material. Although the phenomenon is intensively investigated, important questions such as the exact impact of the mobile ions on the steady-state power conversion efficiency (PCE) and stability remain. Herein, a simple method is proposed to estimate the efficiency loss due to mobile ions via “fast-hysteresis” measurements by preventing the perturbation of mobile ions out of their equilibrium position at fast scan speeds ( ≈ 1000 V s−1). The “ion-free” PCE is between 1% and 3% higher than the steady-state PCE, demonstrating the importance of ion-induced losses, even in cells with low levels of hysteresis at typical scan speeds ( ≈ 100 mV s−1). The hysteresis over many orders of magnitude in scan speed provides important information on the effective ion diffusion constant from the peak hysteresis position. The fast-hysteresis measurements are corroborated by transient charge extraction and capacitance measurements and numerical simulations, which confirm the experimental findings and provide important insights into the charge carrier dynamics. The proposed method to quantify PCE losses due to field screening induced by mobile ions clarifies several important experimental observations and opens up a large range of future experiments. 

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/solr.202100772

Quantification of Efficiency Losses Due to Mobile Ions in Perovskite Solar Cells via Fast Hysteresis Measurements

Ion migration in perovskite layers can significantly reduce the long-term stability of the devices. While perovskite composition engineering has proven an interesting tool to mitigate ion migration, many optoelectronic devices require a specific bandgap and thus require a specific perovskite composition. Here, we look at the effect of grain size to mitigate ion migration. We find that in MAPbBr3 solar cells prepared with grain sizes varying from 2 to 11 μm the activation energy for bromide ion migration increases from 0.17 to 0.28 eV. Moreover, we observe the appearance of a second bromide ion migration pathway for the devices with largest grain size, which we attribute to ion migration mediated by the bulk of the perovskite, as opposed to ion migration mediated by the grain boundaries. Together, these results suggest the beneficial nature of grain engineering for reduction of ion migration in perovskite solar cells.

Isabel Koschany

Papers

Grain Size Influences Activation Energy and Migration Pathways in MAPbBr3 Perovskite Solar Cells.

Ion Migration in Lead Halide Perovskite Solar Cells – Looking at Composition, Dimensionality and Crystallinity