We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FACsSnPbI, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FACsPb(IBr) material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable "all-perovskite" thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

As the record single-junction efficiencies of perovskite solar cells now rival those of CIGS, CdTe, and multicrystalline silicon, they are becoming increasingly attractive for use in tandem solar cells, due to their wide, tunable bandgap and solution processability. Previously, perovskite/silicon tandems were limited by significant parasitic absorption and poor environmental stability. Here, we improve the efficiency of monolithic, two-terminal, 1 cm 2 perovskite/silicon tandems to 23.6% by combining an infrared-tuned silicon heterojunction bottom cell with the recently developed cesium formamidinium lead halide perovskite. This more stable perovskite tolerates deposition of a tin oxide buffer layer via atomic layer deposition that prevents shunts, has negligible parasitic absorption, and allows for the sputter deposition of a transparent top electrode. Furthermore, the window layer doubles as a diffusion barrier, increasing the thermal and environmental stability to enable perovskite devices that withstand a 1000-hour damp heat test at 85 °C and 85% relative humidity.

Wide–band gap metal halide perovskites are promising semiconductors to pair with silicon in tandem solar cells to pursue the goal of achieving power conversion efficiency (PCE) greater than 30% at low cost. However, wide–band gap perovskite solar cells have been fundamentally limited by photoinduced phase segregation and low open-circuit voltage. We report efficient 1.67–electron volt wide–band gap perovskite top cells using triple-halide alloys (chlorine, bromine, iodine) to tailor the band gap and stabilize the semiconductor under illumination. We show a factor of 2 increase in photocarrier lifetime and charge-carrier mobility that resulted from enhancing the solubility of chlorine by replacing some of the iodine with bromine to shrink the lattice parameter. We observed a suppression of light-induced phase segregation in films even at 100-sun illumination intensity and less than 4% degradation in semitransparent top cells after 1000 hours of maximum power point (MPP) operation at 60°C. By integrating these top cells with silicon bottom cells, we achieved a PCE of 27% in two-terminal monolithic tandems with an area of 1 square centimeter.

All-perovskite–based polycrystalline thin-film tandem solar cells have the potential to deliver efficiencies of >30%. However, the performance of all-perovskite–based tandem devices has been limited by the lack of high-efficiency, low–band gap tin-lead (Sn-Pb) mixed-perovskite solar cells (PSCs). We found that the addition of guanidinium thiocyanate (GuaSCN) resulted in marked improvements in the structural and optoelectronic properties of Sn-Pb mixed, low–band gap (~1.25 electron volt) perovskite films. The films have defect densities that are lower by a factor of 10, leading to carrier lifetimes of greater than 1 microsecond and diffusion lengths of 2.5 micrometers. These improved properties enable our demonstration of >20% efficient low–band gap PSCs. When combined with wider–band gap PSCs, we achieve 25% efficient four-terminal and 23.1% efficient two-terminal all-perovskite–based polycrystalline thin-film tandem solar cells.

Two advances that address the main challenges of all-perovskite two-terminal tandem solar cell fabrication are reported. First, a nucleation layer is used to enable high-quality atomic layer deposition-based recombination layers that reduce electronic losses. Second, cation tuning is used for wide-band-gap perovskite solar cells that produce high, stable voltages. Combining these advances allows us to fabricate tandem perovskite solar cells on both rigid and flexible plastic substrates that have high efficiency and promising stability.