In the quest for advancing photovoltaic efficiency, the adoption of multijunction solar cell architectures has emerged as a promising approach. Perovskite/silicon double-junction solar cells have already achieved efficiencies surpassing 33%, exceeding the theoretical efficiency limit for single-junction devices. To enhance efficiency even further, exploring perovskite/perovskite/silicon (PPS) triple-junction solar cells seems a logical next step, as they offer the potential to further reduce thermalization losses and achieve even higher efficiencies. This study delves into the potential of various configurations of PPS modules, exploring different subcell interconnections. Initially, we present an optoelectrical model to simulate the performance of these devices, incorporating both luminescence coupling and cell-to-module losses. This enables us to optimize the bandgap energy of the top and middle perovskite subcells under both standard test conditions (STC) and outdoor conditions. Our analysis reveals that the addition of a perovskite subcell can improve the STC efficiency up to 9%–13%. This gain in STC performance also translates into a similar gain in energy yield, meaning that triple-junction devices produce 8%–14% more electricity than their double-junction reference devices.

We present a new version of our optical model for solar cell simulation: GenPro4. Its working principles are briefly explained. The model is suitable for quickly and accurately simulating a wide range of wafer-based and thin-film solar cells. Especially adjusting layer thicknesses to match the currents in multijunction devices can be done with a minimum of computational cost. To illustrate this, a triple junction thin-film silicon solar cell is simulated. The simulation results show very good agreement with external quantum efficiency measurements. The application of an MgF₂ antireflective coating or an antireflective foil with pyramid texture is considered. Their effects on the implied photocurrents of top, middle, and bottom cells are investigated in detail.