Nanoscale Graded Nitrogen‐Doping of TiO₂ via Pulsed Laser Deposition for Enhancing Charge Transfer in Perovskite Solar Cells

Abstract An electron transport layer (ETL) for highly efficient perovskite solar cells (PSCs) should exhibit superior electrical transport properties and have its band levels aligned with interfacing layers to ensure efficient extraction of photo‐generated carriers. Nitrogen‐doped TiO₂ (TiO₂:N) is considered a promising ETL because it offers higher electrical conductivity compared to conventional ETLs made from spray‐pyrolyzed TiO₂. However, the application of highly doped TiO₂:N in PSCs is often limited by the misalignment of energy band levels with adjacent layers and reduced optical transparency. In this study, a novel approach is introduced to enhance the charge transport characteristics and accurately align the electronic band alignment of TiO₂:N layer through nanoscale doping level grading, achieved through the pulsed laser deposition (PLD) technique. The TiO₂:N ETL with a graded doping profile can combine characteristics of both highly doped and lightly doped phases on each side. Furthermore, a nanoscale doping gradation, employing an ultrathin sub‐layer structure with graded doping levels, creates a smoothly cascading band‐level alignment that bridges the adjacent layers, enhancing the transport of photo‐generated carriers. Consequently, this method leads to a substantial increase in the power conversion efficiency (PCE), exceeding 22%, which represents a relative improvement of 11% compared to traditional spray‐pyrolyzed TiO₂‐based PSCs.