Tandem solar cells that pair silicon with a metal halide perovskite are a promising option for surpassing the single-cell efficiency limit. We report a monolithic perovskite/silicon tandem with a certified power conversion efficiency of 29.15%. The perovskite absorber, with a bandgap of 1.68 electron volts, remained phase-stable under illumination through a combination of fast hole extraction and minimized nonradiative recombination at the hole-selective interface. These features were made possible by a self-assembled, methyl-substituted carbazole monolayer as the hole-selective layer in the perovskite cell. The accelerated hole extraction was linked to a low ideality factor of 1.26 and single-junction fill factors of up to 84%, while enabling a tandem open-circuit voltage of as high as 1.92 volts. In air, without encapsulation, a tandem retained 95% of its initial efficiency after 300 hours of operation.

The performance of perovskite solar cells (PSCs) is predominantly limited by non-radiative recombination, either through trap-assisted recombination in the absorber layer or via minority carrier recombination at the perovskite/transport layer interfaces. Here we use transient and absolute photoluminescence imaging to visualize all non-radiative recombination pathways in planar pin-type PSCs with undoped organic charge transporting layers. We find significant quasi-Fermi level splitting losses (135 meV) in the perovskite bulk, while interfacial recombination results in an additional free energy loss of 80 meV at each individual interface which limits the open-circuit voltage ( OC ) of the complete cell to ~1.12 V. Inserting ultrathin interlayers between the perovskite and transport layers allows substantial reduction of these interfacial losses at both the p and n contacts. Using this knowledge and approach, we demonstrate reproducible dopant-free 1 cm 2 PSCs surpassing 20% efficiency (19.83% certified) with stabilized power output, a high OC (1.17 V) and record fill factor (> 81%).

We introduce new hole-selective contacts for next-generation perovskite photovoltaics and point to design paths for molecular engineering of perfect interfaces.

We quantify recombination losses in the bulk and interfaces for different perovskite compositions and popular charge transport layers.

We demonstrate open-circuit voltages exceeding 1.26 V for CH3NH3PbI3 solar cells by careful process optimization of the perovskite and its interfaces to the electron and hole transport layers. This open-circuit voltage is the highest reported so far in a full MAPI cell stack and only 64 mV below the maximum open circuit voltage that is possible for this material. We confirm these values for the open circuit voltage by independent measurements of the external photoluminescence quantum efficiency reaching values of 5 % for the fully processed solar cell. We further find exceptionally long photoluminescence lifetimes in full cells and in layer stacks involving one or two contact layers. Numerical simulations reveal that these long photoluminescence lifetimes are only possible with extremely low interface recombination velocities between absorber and contact materials.