Funder: UNIQUEFunder: National University of Ireland Travelling StudentshipFunder: Engineering and Physical Sciences Research Council; Id: http://dx.doi.org/10.13039/501100000266Funder: Cambridge Trust ScholarshipFunder: Robert Gardiner ScholarshipCarbon-based electrodes represent a promising approach to improve stability and up-scalability of perovskite photovoltaics. The temperature at which these contacts are processed defines the absorber grain size of the perovskite solar cell: in cells with low-temperature carbon-based electrodes (L-CPSCs), layer-by-layer deposition is possible, allowing perovskite crystals to be large (>100 nm), while in cells with high-temperature carbon-based contacts (H-CPSCs), crystals are constrained to 10-20 nm size. To enhance the power conversion efficiency of these devices, the main loss mechanisms were identified for both systems. Measurements of charge carrier lifetime, quasi-Fermi level splitting (QFLS) and light-intensity-dependent behavior, supported by numerical simulations, clearly demonstrate that H-CPSCs strongly suffer from non-radiative losses in the perovskite absorber, primarily due to numerous grain boundaries. In contrast, large crystals of L-CPSCs provide long carrier lifetime (1.8 µs) and exceptionally high QFLS of 1.21 eV for an absorber bandgap of 1.6 eV. These favorable characteristics explain the remarkable open-circuit voltage (VOC) of over 1.1 V in hole-selective layer-free L-CPSCs. However, the low photon absorption and poor charge transport in these cells limit their potential. Finally, effective strategies are provided to reduce non-radiative losses in H-CPSCs, transport losses in L-CPSCs and to improve photon management in both cell types.This work has been partially funded within the projects PROPER financed from the German Ministry of Education and Research under funding number 01DR19007 and UNIQUE supported under umbrella of SOLAR-ERA.NET_cofund by ANR, PtJ, MIUR, MINECO-AEI and SWEA, within the EU's HORIZON 2020 Research and Innovation Program (cofund ERA-NET Action No. 691664). D. B. acknowledges the scholarship support of the German Federal Environmental Foundation (DBU) and S. Z. acknowledges the scholarship support of the German Academic Exchange Service (DAAD). B.Y. and A.Ha. acknowledge the funding from the European Union’s Horizon 2020 research and innovation program ESPRESSO under the agreement No.: 764047. This work has also been partially funded by Swiss National Science Foundation with Project No. 200020_185041. T.D. acknowledges a National University of Ireland Travelling Studentship. K.F. acknowledges a George and Lilian Schiff Studentship, Winton Studentship, the Engineering and Physical Sciences Research Council (EPSRC) studentship, Cambridge Trust Scholarship, and Robert Gardiner Scholarship. S.S. acknowledges support from the Royal Society and Tata Group (UF150033). M.A. acknowledges funding from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No.841386. The authors would like to thank Maryamsadat Heydarian and Laura Stevens for their EQE and AFM measurements. The authors thank the EPSRC (EP/R023980/1) for funding
