The Modification of Nitrogen to Modulate Perovskite for the Application of p-Type Transparent Conductive Oxides

Due to the strong electronegativity of oxygen ions, the valence band maximum (VBM) that is derived from the O 2p orbital leads to strong localization, as well as further heavy hole mass and low hole mobility, which makes it extremely difficult to obtain high-conductivity p-type transparent conductive materials. Herein, we propose the strategy of multiple anions through the introduction of weaker electronegative nitrogen, in consideration of the delocalization on VBM, as well as the stability of octahedral anion cages. As such, first-principles calculations in the framework of density functional theory (DFT) are used for this work. Crystal structure prediction software USPEX (version 2023.0) was adopted to investigate the N-O appropriate ratio in CaTiO3−xNx (0 ≤ x ≤ 1) to balance the high transmission of light and highly favorable dispersion at the VBM. Furthermore, the p-type TCO performance of CaTiO3-xNx was evaluated based on the hole effective mass, hole mobility, and conductivity. The effectiveness of modulating p-type TCO through N-O multiple anions was also evaluated through defect formation energy and ionization energy. Ultimately, the construction of a CaTiO3-xNx/Si heterojunction and band alignment were considered for practical application. This approach attempts to boost the diversity of p-type perovskite-based TCOs and opens a new perspective for engineering and innovative material design for sustainable TCOs demand.