Green Anisole Solvent-Based Synthesis and Deposition of Phthalocyanine Dopant-Free Hole-Transport Materials for Perovskite Solar Cells

Perovskite Solar Cells (PSCs) have attracted attention due to their low cost, easy solution processability, high efficiency, and scalability. However, the benchmark expensive hole transport material (HTM) 2,2?,7,7?-tetrakis[N, N-di(4-methoxyphenyl)amino]-9,9?-spirobifluorene (Spiro-MeOTAD), which is traditionally solution-processed with toxic solvents such as chlorobenzene (CB), dichlorobenzene (DCB), or toluene, is a bottleneck. To address this issue, this work investigates the implementation of Zn(II), Cu(II), or Co(II) tetra-tert-butylphthalocyanines (TBU4-Cu, TBU4-Zn, TBU4-Co), established macrocyclic derivatives whose synthesis and processing inside the devices have been redesigned to be more environmentally sustainable and cost-effective by substituting conventional solvents with greener alternatives such as anisole, propane-1,2-diol, and their mixture, as dopant-free HTMs in planar n-i-p PSCs. The anisole-processed HTMs provided power conversion efficiencies (PCE) up to 12.27% for TBU4-Cu and 11.73% for TBU4-Zn, with better photovoltaic parameters than the corresponding cells made with chlorobenzene for which the best results obtained were, respectively, 12.22% and 10.81%.