PEDOT:PSS is commonly used as a hole transport layer in perovskite solar cells because it combines high transparency, good conductivity, and suitable energy-level alignment, but its moisture sensitivity and acidity can damage perovskite layers and limit long-term stability. In contrast, replacing it with a phenothiazine-based self-assembled monolayer allows better interfacial control during crystallization, lowers defect densities, and enables highly efficient all-perovskite tandem devices with a reported efficiency of 29.1%.