promising light absorber materials, demon strating low-cost solution processing, ease of fabrication, and outstanding optoelectronic properties. [1,2] Since the first report on the perovskite solar cells (PSCs) employing methylammonium lead iodide (MAPbI 3 ), [3] their power conversion efficiency (PCE) has now exceeded 25% for small-area cells. [4,5] The high efficiency of PSCs is achieved by tuning the perovskite layer through compositional engineering, [6][7][8] surface passivation, [9][10][11][12][13] and/or by using various additives. [14][15][16] Besides component engineering of the perovskite layer, a lot of works have been devoted to the development of efficient charge transport layers. [17][18][19][20][21] Particularly, the electron transport layers (ETLs) play an important role in realizing efficient and stable PSCs. [22,23] Thus far, titanium dioxide (TiO 2 ) is a widely applied ETL in PSCs but it suffers from low conductivity and high surface defect density. [24] Among alternative ETLs, zinc oxide (ZnO) has been regarded as a convenient candidate due to its high electron mobility and well-matched energy level with perovskite material. [25,26] This Atomic layer deposition (ALD) has been considered as an efficient method to deposit high quality and uniform thin films of various electron transport materials for perovskite solar cells (PSCs). Here, the effect of deposition sequence in the ALD process of aluminum-doped zinc oxide (AZO) films on the performance and stability of PSCs is investigated. Particularly, the surface of AZO film is terminated by diethylzinc (DEZ)/H 2 O (AZO-1) or trimethylaluminum (TMA)/H 2 O pulse (AZO-2), and investigated with surface-sensitive X-ray photoelectron spectroscopy technique. It is observed that AZO-2 significantly enhances the thermal stability of the upcoming methylammonium lead iodide (MAPbI 3 ) layer and facilitates charge transport at the interface as evidenced by photoluminescence spectroscopes and favorable interfacial band alignment. Finally, planar-type PSC with AZO-2 layer exhibits a champion power conversion efficiency of 18.09% with negligible hysteresis and retains 82% of the initial efficiency after aging for 100 h under ambient conditions (relative humidity 40 ± 5%). These results highlight the importance of atomic layer engineering for developing efficient and stable PSCs.

Despite the impressive progresses, perovskite solar cells (PSCs) employing operationally instable organic hole transporting layers (HTLs) are still far from the upscaling applications. Therefore, the development of new sustainable materials to meet the commercialization requirements is of great urgency. In addition, the high cost resulting from the complex production conditions of organic HTL materials is another limiting factor that must be overcome in the way of commercialization. Although various structures and types of HTL materials have been reported in this context, inorganic‐based materials have attracted the greatest attention both in terms of low‐cost and long‐term stability. However, inorganic HTL‐based cells have not yet reached the efficiency values of organic HTL‐based cells. In this mini Review, it is aimed to evaluate the alternative HTL materials only performing a destructive role in n‐i‐p architecture in terms of cell performance, stability, and cost. Hereof, a general evaluation of the HTL materials reported in the literature has been made and the effects of these materials on the cell performance have been elaborated and discussed.