In this work, we report the benefits of incorporating p h e n e t h y l a m m o n i u m c a t i o n ( P E A + ) i n t o ( H C -(NH 2 ) 2 PbI 3 ) 0.85 (CH 3 NH 3 PbBr 3 ) 0.15 perovskite for the first time. After adding small amounts of PEA cation (<10%), the perovskite film morphology is changed but, most importantly, grain boundaries are passivated. This is supported by Kelvin Probe Force Microscopy (KPFM). The passivation results in the increase in photoluminescence intensity and carrier lifetimes of test structures and open-circuit voltages (V OC ) of the devices as long as the addition of PEA + is ≤4.5%. The presence of higher-band-gap quasi-2D PEA incorporated perovskite is responsible for the grain boundary passivation, and the quasi-2D perovskites are also found to be concentrated near the TiO 2 layer, revealed by PL spectroscopy. Results of moisture exposure tests show that PEA + incorporation is effective in slowing down the degradation of unencapsulated devices compared to the control devices without PEA + . These findings provide insights into the operation of perovskite solar cells when large cations are incorporated.

Layered low‐dimensional perovskite structures employing bulky organic ammonium cations have shown significant improvement on stability but poorer performance generally compared to their 3D counterparts. Here, a mixed passivation (MP) treatment is reported that uses a mixture of bulky organic ammonium iodide (iso‐butylammonium iodide, iBAI) and formammidinium iodide (FAI), enhancing both power conversion efficiency and stability. Through a combination of inactivation of the interfacial trap sites, characterized by photoluminescence measurement, and formation of an interfacial energetic barrier by which ionic transport is reduced, demonstrated by Kelvin probe force microscopy, MP treatment of the perovskite/hole transport layer interface significantly suppresses photocurrent hysteresis. Using this MP treatment, the champion mixed‐halide perovskite cell achieves a reverse scan and stabilized power conversion efficiency of 21.7%. Without encapsulation, the devices show excellent moisture stability, sustaining over 87% of the original performance after 38 d storage in ambient environment under 75 ± 20% relative humidity. This work shows that FAI/iBAI, is a new and promising material combination for passivating perovskite/selective‐contact interfaces.

aMonolithic perovskite/silicon tandem solar cells show great promise for further efficiency enhancement for current silicon photovoltaic technology. In general, an interface (tunnelling or recombination) layer is usually required for electrical contact between the top and the bottom cells, which incurs higher fabrication costs and parasitic absorption. Most of the monolithic perovskite/Si tandem cells demonstrated use a hetero-junction silicon (Si) solar cell as the bottom cell, on small areas only. This work is the first to successfully integrate a low temperature processed (r150 1C) planar CH 3 NH 3 PbI 3 perovskite solar cell on a homo-junction silicon solar cell to achieve a monolithic tandem without the use of an additional interface layer on large areas (4 and 16 cm 2 ).Solution processed SnO 2 has been effective in providing dual functions in the monolithic tandem, serving as an ETL for the perovskite cell and as a recombination contact with the n-type silicon homo-junction solar cell that has a boron doped p-type (p++) front emitter. The SnO 2 /p++ Si interface is characterised in this work and the dominant transport mechanism is simulated using Sentaurus technology computer-aided design (TCAD) modelling. The champion device on 4 cm 2 achieves a power conversion efficiency (PCE) of 21.0% under reverse-scanning with a V OC of 1.68 V, a J SC of 16.1 mA cm À2 and a high FF of 78% yielding a steady-state efficiency of 20.5%. As our monolithic tandem device does not rely on the SnO 2 for lateral conduction, which is managed by the p++ emitter, up scaling to large areas becomes relatively straightforward. On a large area of 16 cm 2 , a reverse scan PCE of 17.6% and a steady-state PCE of 17.1% are achieved. To our knowledge, these are the most efficient perovskite/homo-junction-silicon tandem solar cells that are larger than 1 cm 2 . Most importantly, our results demonstrate for the first time that monolithic perovskite/silicon tandem solar cells can be achieved with excellent performance without the need for an additional interface layer. This work is relevant to the commercialisation of efficient large-area perovskite/homo-junction silicon tandem solar cells. Broader contextA simple approach for integrating a perovskite solar cell monolithically onto a Si solar cell is reported here. The first advantage of this approach is that it does not require additional fabrication of an additional interface layer between the perovskite and Si cell. The second advantage of this approach is that it is compatible with a homo-junction p-n Si solar cell, which is a common Si solar cell structure for commercial cells. The third advantage is that the entire sequence for the planar perovskite cell fabrication is done at low temperatures, minimising damage to the bottom Si solar cell. The fourth advantage is that the SnO 2 electron transport layer of the perovskite top cell also serves as a recombination contact with the silicon bottom cell. Finally, this monolithic tandem approach does not rely on the SnO 2 for lateral conducti...