Stacking solar cells with decreasing band gaps to form tandems presents the possibility of overcoming the single-junction Shockley-Queisser limit in photovoltaics. The rapid development of solution-processed perovskites has brought perovskite single-junction efficiencies >20%. However, this process has yet to enable monolithic integration with industry-relevant textured crystalline silicon solar cells. We report tandems that combine solution-processed micrometer-thick perovskite top cells with fully textured silicon heterojunction bottom cells. To overcome the charge-collection challenges in micrometer-thick perovskites, we enhanced threefold the depletion width at the bases of silicon pyramids. Moreover, by anchoring a self-limiting passivant (1-butanethiol) on the perovskite surfaces, we enhanced the diffusion length and further suppressed phase segregation. These combined enhancements enabled an independently certified power conversion efficiency of 25.7% for perovskite-silicon tandem solar cells. These devices exhibited negligible performance loss after a 400-hour thermal stability test at 85°C and also after 400 hours under maximum power point tracking at 40°C.

Bifacial monolithic perovskite/silicon tandem solar cells exploit albedo-the diffuse reflected light from the environment-to increase their performance above that of monofacial perovskite/silicon tandems. Here we report bifacial tandems with certified power conversion efficiencies >25% under monofacial AM1.5G 1 sun illumination that reach power-generation densities as high as ~26 mW cm -2 under outdoor testing. We investigated the perovskite bandgap required to attain optimized current matching under a variety of realistic illumination and albedo conditions. We then compared the properties of these bifacial tandems exposed to different albedos and provide energy yield calculations for two locations with different environmental conditions. Finally, we present a comparison of outdoor test fields of monofacial and bifacial perovskite/silicon tandems to demonstrate the added value of tandem bifaciality for locations with albedos of practical relevance.

Sputtered nickel oxide (NiOx) is an attractive hole‐transport layer for efficient, stable, and large‐area p‐i‐n metal‐halide perovskite solar cells (PSCs). However, surface traps and undesirable chemical reactions at the NiOx/perovskite interface are limiting the performance of NiOx‐based PSCs. To address these issues simultaneously, an efficient NiOx/perovskite interface passivation strategy by using an organometallic dye molecule (N719) is reported. This molecule concurrently passivates NiOx and perovskite surface traps, and facilitates charge transport. Consequently, the power conversion efficiency (PCE) of single‐junction p‐i‐n PSCs increases from 17.3% to 20.4% (the highest reported value for sputtered‐NiOx based PSCs). Notably, the N719 molecule self‐anchors and conformally covers NiOx films deposited on complex surfaces. This enables highly efficient textured monolithic p‐i‐n perovskite/silicon tandem solar cells, reaching PCEs up to 26.2% (23.5% without dye passivation) with a high processing yield. The N719 layer also forms a barrier that prevents undesirable chemical reactions at the NiOx/perovskite interface, significantly improving device stability. These findings provide critical insights for improved passivation of the NiOx/perovskite interface, and the fabrication of highly efficient, robust, and large‐area perovskite‐based optoelectronic devices.

Perovskite light-emitting diodes (LEDs) have attracted broad attention due to their rapidly increasing external quantum efficiencies (EQEs) [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] . However, most high EQEs of perovskite LEDs are reported at low current densities (< 1 mA cm -2 ) and low brightness. Decrease in efficiency and rapid degradation at high brightness inhibit their practical applications. Here,