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Development of all-inorganic perovskite solar cells (PSCs) is highly desirable due to its excellent thermal stability and great potential for tandem solar cells. One main bottleneck that restricts its further development is the absence of the ideal hole-transporting materials which is critical to device performance and stability. Herein, we construct a brand-new architecture of all-inorganic PSCs via employing a series of doping-free polymeric organic photovoltaic donor materials as hole transport materials including J71, PBDB-T, PM6 with suitable energy level and carrier transport ability. The mechanism in terms of film molecular microscopic structure, electrical transport dynamics, electrical potential distribution were systematically investigated by grazing incidence wide-angle X-ray scattering (GIWAXS), conductive atomic force microscope (C-AFM) and kelvin probe force microscopy (KPFM) measurements. This work not …