Mixed halide hybrid perovskites are of significant interest because their bandgap can be tuned as a current-matched top-cell in tandem photovoltaics. However, several mixed halide perovskites phase segregate under illumination, exhibit large voltage deficits, and produce unstable photocurrents. We investigate the origin of phase segregation and implication for tandems with mixed halide large-bandgap (∼1.75 eV) perovskites. We show explicitly that MAPb­(I0.6Br0.4)3 and (MA0.9,Cs0.1)­Pb­(I0.6,Br0.4)3, termed “MA” and “MACs”, respectively, rapidly phase segregate in the dark upon 1 sun equivalent current injection. This is direct experimental evidence that conduction band electrons or valence band holes are the culprit behind phase segregation. In contrast, (FA0.83,Cs0.17)­Pb­(I0.66,Br0.34)3, or “FACs,” prepared at only 75 °C resists phase segregation below 4 sun injection. FACs prepared at 165 °C yields larger grains and withstands higher injected carrier concentrations before phase segregation. The FACs and MACs devices sustain near constant power output at 1 sun and do not affect the current output of a CIGS bottom cell when used as an incident light filter.

No abstract

The open-circuit voltages (V OC) of hybrid perovskite (HP) solar cells do not increase sufficiently with increasing bandgap (for Eg > 1.70eV). We study the impact of A+ size mismatch induced lattice distortions (in ABX3 structure) on the optoelectronic quality of high-bandgap HPs and find that the highest quality films have high A-site size-mismatch, where large guanidinium (GA) compensates for small Cs to keep the tolerance factor in the range for the perovskite structure. Specifically, we find that 1.84eV bandgap (FA0.33GA0.19Cs0.47)­Pb­(I0.66Br0.34)3 and 1.75eV bandgap (FA0.58GA0.10Cs0.32)­Pb­(I0.73Br0.27)3 attain quasi-Fermi level splitting of 1.43eV and 1.35eV, respectively, which is >91% of the Shockley-Queisser limit for both cases. Films of 1.75eV bandgap (FA,GA,Cs)­Pb­(I,Br)3 are then used to fabricate p-i-n photovoltaic devices that have a V OC of 1.24 V. This V OC is among the highest V OC reported for any HPs with similar bandgap (1.7 to 1.8 eV) and a substantial improvement for the p-i-n architecture, which is desirable for tandems with Si, CIGS, or a low-bandgap HP. Collectively, our results show that non-radiative recombination rates are reduced in (FA,GA,Cs)­Pb­(I,Br)3 films and prove that FA-GA-Cs alloying is a viable route to attain high V OC in high-bandgap HP solar cells.