High bandgap perovskite solar cells are integral to perovskite‐based multi‐junction tandem solar cells with efficiency potentials over 40%. However, at present, high bandgap perovskite devices underperform compared to their mid bandgap counterparts in terms of voltage outputs and fill factors resulting in lower than ideal efficiencies. Here, the low fill factor aspect of high bandgap perovskite is addressed by developing a cation‐diffusion‐based double‐sided interface passivation scheme that simultaneously provides bulk passivation for a 1.75 eV perovskite cell that is also compatible with a p‐i‐n cell architecture. The champion cell achieves a record fill factor of 86.5% and a power conversion efficiency of 20.2%. Results of ionic distribution profiling, Fourier transform infrared spectroscopy, and X‐ray diffraction crystallography reveal evidence of cation diffusion from the surface perovskite passivation layer into bulk. The diffused cations reduce Shockley–Read–Hall recombination in the perovskite bulk and at the surfaces with the latter being more dominant as confirmed by light‐intensity dependent and temperature‐dependent open‐circuit voltage measurements as well as thermal admittance spectroscopy. This concurrent bulk and surface passivation scheme renders record fill factor and efficiency in the double‐side passivated cells. This provides new insights for future passivation strategies based on ionic diffusion of functionalized materials.

All-solid-state lithium batteries (ASSLBs) based on sulfide solid electrolytes (SEs) have received great attention because of the high ionic conductivity of the SEs, intrinsic thermal safety, and higher energy density achievable with a Li metal anode. However, studies on practical slurry-cast composite electrodes show an extremely limited battery performance than the binder-free pelletized electrodes because of the poor interfacial robustness between the active materials and SEs by the presence of a polymeric binder. Here, we employ a low-temperature post-sintering process for the slurry-cast composite electrodes in order to overcome the binder-induced detrimental effects on the electrochemical performance. The LiI-doped LiPS SEs are chosen because the addition of iodine not only improves the Li-ion conductivity and Li metal compatibility but also lowers the glass-transition and crystallization temperatures. Low-temperature post-sintering of composite cathodes consisting of a LiNiCoMnO-active material, LiI-doped LiPS SE, polymeric binder, and conducting agent shows a significantly improved electrochemical performance as compared to a conventional slurry-cast electrode containing pre-annealed SEs. Detailed analyses by electrochemical impedance spectroscopy and galvanostatic intermittent titration technique confirm that post-sintering effectively reduces the interfacial resistance and enhances the chemomechanical robustness at solid-solid interfaces, which enables the development of practical slurry-cast ASSLBs with sulfide SEs.

The tandem cell structure is the most promising solution for the next generation photovoltaic technology to overcome the single‐junction Shockley–Queisser limit. The fabrication of a perovskite/c‐Si monolithic tandem device has not yet been demonstrated on a c‐Si bottom cell produced from an industrial production line. Here, a c‐Si cell with a tunneling oxide passivating contact (TOPCon) structure produced on a production line as the bottom cell of a tandem device, and a top cell featuring solution‐processed perovskite films to form the tandem device are used. The c‐Si cell features a rough damage etched, but untextured front surface from the wafering processes. To combat the challenge of rough surfaces, several strategies to avoid shunt paths across carrier transport layers, absorber layers, and their interfaces are implemented. Moreover, the origin of reflection loss on this planar structure is investigated and the reflection loss is managed to below 4 mA cm−2. In addition, the source of the voltage loss from the TOPCon bottom cell is identified and the device structure is redesigned to be suitable for tandem applications while still using mass production feasible fabrication methods. Overall, 27.6% efficiency is achieved for a monolithic perovskite/c‐Si tandem device, with significant potential for future improvements.

One of the important factors in the performance of perovskite solar cells (PSCs) is effective defect passivation. Dimensional engineering technique is a promising method to efficiently passivate non‐radiative recombination pathways in the bulk and surface of PSCs. Herein, a passivation approach for the perovskite/hole transport layer interface is presented, using a mixture of guanidinium and n‐octylammonium cations introduced via GuaBr and n‐OABr. The dual‐cation passivation layer can provide an open‐circuit voltage of 1.21 V with a power conversion efficiency of 23.13%, which is superior to their single cation counterparts. The mixed‐cation passivation layer forms a 1D/2D perovskite film on top of 3D perovskite, leading to a more hydrophobic and smoother surface than the uncoated film. A smooth surface can diminish non‐radiative recombination and enhance charge extraction at the interface making a better contact with the transport layer, resulting in improved short‐circuit current. In addition, space charge‐limited current measurements show a three times reduction in the trap‐filled limit voltage in the mixed‐cation passivated sample compared with unpassivated cells, indicating fewer trapped states. The shelf‐life stability test in ambient atmosphere with 60% relative humidity as well as light‐soaking stability reveal the highest stability for the dual‐cation surface passivation.

Halide-doped sulfide solid electrolytes have attracted great attention due to their high lithium-ion conductivity, Li-metal compatibility, and deformability for use in all-solid-state Li batteries. Although the effects of halide mixing in Li 6 PS 5 X and Li 4 PS 4 X (X = halogen) solid electrolytes are fully investigated, studies on the origin of the remarkable increase in the ionic conductivity by dual halide doped Li 7 P 2 S 8 X (X = I, Br) solid electrolytes are scarce. Here, we systematically investigate the crystal phase evolution in glassy matrix and the corresponding ionic conductivity variation, revealing that a metastable Li 10 GeP 2 S 12 -like Li 3 PS 4 phase with halide-doped glassy matrix is responsible for the outstanding performance.