As the most promising lead‐free one, tin‐halides based perovskite solar cells still suffer from the severe bulk‐defect due to the easy oxidation of tin from divalent to tetravalent. Here, a general and effective strategy is delivered to modulate the microstructure of 2D/3D heterogeneous tin‐perovskite absorber films by substituting FAI with FPEABr in FASnI3. The introduction of 2D phase can induce highly oriented growth of 3D FASnI3 and it is revealed in the optimal 2D/3D film that 2D phase embraces 3D grains and locates at the surfaces and grain boundaries. The FPEA+ based 2D tin‐perovskite capping layer can offer a reducing atmosphere for vulnerable 3D FASnI3 grains. The unique microstructure effectively suppresses the well‐known oxidation from Sn2+ to Sn4+, as well as decreasing defect density, which leads to a remarkable enhanced device performance from 9.38% to 14.81% in conversion efficiency. The certified conversion efficiency of 14.03% announces a new record and moves a remarkable step from the last one (12.4%). Besides of this breakthrough, this work definitely paves a new way to fabricate high‐quality tin‐perovskite absorber film by constructing effective 2D/3D microstructures.

Hole‐transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long‐term stability, high‐performance dopant‐free small‐molecule HTMs (SM‐HTMs) are greatly desired. However, such dopant‐free SM‐HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor–acceptor‐type SM‐HTMs (MPA‐BTI and MPA‐BTTI) are devised, which synergistically integrate several design principles for high‐performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant‐free MPA‐BTTI‐based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long‐term stability under illumination, which breaks the long‐time standing bottleneck in the development of dopant‐free SM‐HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well‐aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA‐BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high‐performance dopant‐free SM‐HTMs in PVSCs.

In this work, significant suppression of the interfacial recombination by facile alkali chloride interface modification of the NiOx hole transport layer in inverted planar perovskite solar cells is achieved. Experimental and theoretical results reveal that the alkali chloride interface modification results in improved ordering of the perovskite films, which in turn reduces defect/trap density, causing reduced interfacial recombination. This leads to a significant improvement in the open‐circuit voltage from 1.07 eV for pristine NiOx to 1.15 eV for KCl‐treated NiOx, resulting in a power conversion efficiency approaching 21%. Furthermore, the suppression of the ion diffusion in the devices is observed, as evidenced by stable photoluminescence (PL) under illumination and high PL quantum efficiency with alkali chloride treatment, as opposed to the luminescence enhancement and low PL quantum efficiency observed for perovskite on pristine NiOx. The suppressed ion diffusion is also consistent with improved stability of the devices with KCl‐treated NiOx. Thus, it is demonstrated that a simple interfacial modification is an effective method to not only suppress interfacial recombination but also to suppress ion migration in the layers deposited on the modified interface due to improved interface ordering and reduced defect density.

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