TiCl₄precursor affecting the performance of HTM-free carbon-based perovskite solar cell

The presence of TiO₂used as an efficient electron transport layer is crucial to achieving high-performance solar cells, especially for a hole transport material (HTM)-free carbon-based perovskite solar cell (PSC). The hydrolysis of TiCl₄is one of the most widely used routes for forming TiO₂layer in solar cells, which includes the stock solution preparation from TiCl₄initial precursor and the thermal hydrolysis of the stock solution. The second thermal hydrolysis step has been extensively studied, while the initial hydrolysis reaction in the first step is not receiving sufficient attention, especially for its influence on the photovoltaic performance of HTM-free carbon-based devices. In this study, the role of TiCl₄stock solution in the growth process of TiO₂layer is examined. Based on the analysis of the Ti(IV) intermediate states for different TiCl₄concentrations from Raman spectra, 2 M TiCl₄precursor exhibits moderate nucleation and growth kinetics without generating too many intermediates which occurs in 3 M TiCl₄precursor, yielding ∼300 nm size spherical TiO₂agglomerates with a rutile phase. In the aspect of devices, the HTM-free carbon-based PSCs fabricated using 2 M TiCl₄precursor deliver a conversion efficiency beyond 17%, which may be attributed to the reduced defect in compact TiO₂layer.