In this work, a fully tin‐based, mixed‐organic‐cation perovskite absorber (FA)x(MA)1− xSnI3 (FA = NH2CH = NH2 +, MA = CH3NH3 +) for lead‐free perovskite solar cells (PSCs) with inverted structure is presented. By optimizing the ratio of FA and MA cations, a maximum power conversion efficiency of 8.12% is achieved for the (FA)0.75(MA)0.25SnI3‐based device along with a high open‐circuit voltage of 0.61 V, which originates from improved perovskite film morphology and inhibits recombination process in the device. The cation‐mixing approach proves to be a facile method for the efficiency enhancement of tin‐based PSCs.

Although inorganic hole-transport materials usually possess high chemical stability, hole mobility, and low cost, the efficiency of most of inorganic hole conductor-based perovskite solar cells is still much lower than that of the traditional organic hole conductor-based cells. Here, we have successfully fabricated high quality CH3NH3PbI3 films on top of a CuSCN layer by utilizing a one-step fast deposition-crystallization method, which have lower surface roughness and smaller interface contact resistance between the perovskite layer and the selective contacts in comparison with the films prepared by a conventional two-step sequential deposition process. The average efficiency of the CuSCN-based inverted planar CH3NH3PbI3 solar cells has been improved to 15.6% with a highest PCE of 16.6%, which is comparable to that of the traditional organic hole conductor-based cells, and may promote wider application of the inexpensive inorganic materials in perovskite solar cells.

It is extremely significant to study the trap state passivation and minimize the trap states of perovskite to achieve high-performance perovskite solar cells (PSCs). Here, we have first revealed and demonstrated that a novel p-type conductor Cu(thiourea)I [Cu(Tu)I] incorporated in perovskite layer can effectively passivate the trap states of perovskite via interacting with the under-coordinated metal cations and halide anions at the perovskite crystal surface. The trap state energy level of perovskite can be shallowed from 0.35-0.45 eV to 0.25-0.35 eV. In addition, the incorporated Cu(Tu)I can participate in constructing the p-i bulk heterojunctions with perovskite, leading to an increase of the depletion width from 126 to 265 nm, which is advantageous for accelerating hole transport and reducing charge carrier recombination. For these two synergistic effects, Cu(Tu)I can play a much better role than that of the traditional p-type conductor CuI, probably due to its identical valence band maximum with that of perovskite, which enables to not only lower the trap state energy level to a greater extent but also eliminate the potential wells for holes at the p-i heterojunctions. After optimization, a breakthrough efficiency of 19.9% has been obtained in the inverted PSCs with Cu(Tu)I as the trap state passivator of perovskite.