Organic–inorganic lead halide perovskite absorbers in combination with electron and hole transporting selective contacts result in power conversion efficiencies of over 23% under AM 1.5 sun conditions. The advantage of perovskite solar cells is their simple fabrication through solution-processing methods either in n-i-p or p-i-n configurations. Using TiO₂ or SnO₂ as an electron transporting layer, a compositionally engineered perovskite as an absorber layer, and Spiro-OMeTAD as a HTM, several groups have reported over 20% efficiency. Though perovskite solar cells reached comparable efficiency to that of crystalline silicon ones, their stability remains a bottleneck for commercialization partly due to the use of doped Spiro-OMeTAD. Several organic and inorganic hole transporting materials have been explored to increase the stability and power conversion efficiency of perovskite solar cells. IIn this review, we analyse the stability and efficiency of perovskite solar cells incorporating phthalocyanine and porphyrin macrocycles as hole- and electron transporting materials. The π–π stacking orientation of these macrocycles on the perovskite surface is important in facilitating a vertical charge transport, resulting in high power conversion efficiency.

A non-aggregated Zn(II)octa(2,6-diphenylphenoxy) phthalocyanine (coded as TT80) has been used as a hole-transporting material for perovskite solar cells. The cells were fabricated under three different configurations by changing the uptake solvent (chlorobenzene or toluene) and incorporating additives (bis(trifluoromethane) sulfonimide lithium salt (LiTFSI) and 4-tert-butylpyridine (TBP). A power conversion efficiency of 6.7% (AM1.5G standard conditions) was achieved for the best cell under optimized configuration.

Owing to the complementarity between a bis-Zn(II)–porphyrin receptor and a fullerene ligand bearing two pyridine substituents, the substrate can be clicked onto the ditopic receptor, thus leading to a stable non-covalent macrocyclic 1 ∶ 1 complex.