Effects of transition metals incorporated into perovskite crystals on the electronic structures and magnetic properties by first-principles calculation

Abstract

Additive effects of transition metals (M = Cr2+, Co2+, Cu2+ and Y3+) on the electronic structures and magnetic properties of formamidinium lead halide perovskite compounds (FAPbI3, where FA = NH2CHNH2+) were investigated by first-principle calculation using density functional theory. In the case of Cr2+, Cu2+ and Y3+-incorporated FAPbI3 perovskite crystals, the electron density distribution of d-p hybrid orbital on the transition metal and iodine halogen-atoms were delocalized at frontier orbital. The total and partial density of state appeared the 3d-p hybrid orbital near the frontier orbital with narrowing band gap, yielding the wide broad absorption in the near-infrared region. The electronic correlation worked in between the localized spin on 3d orbital of the metal, and the itinerant carriers on the 5p orbital of the iodine halogen ligand and the 6p orbital of the lead atom in the perovskite crystal. The vibration behavior of the Raman and Infrared spectra were associated with change of polarization and slight distortion near the coordination structure. The considerable splitting of chemical shift of 127I-NMR and 207Pb-NMR in the Co2+ and Cu2+-incorporated FAPbI3 crystals were caused by crystal field splitting as Jahn-Teller effect with nearest-neighbor nuclear quadrupole interaction based on the charge distribution.

Photocatalysis and perovskite oxide-based materials: a remedy for a clean and sustainable future

“…The high atomic energy of the transition metal ensures better electron mobility without changing conduction band minima of perovskite host material. 96 …”

Effects of mixed-valence states of Eu-doped FAPbI3 perovskite crystals studied by first-principles calculation

“…[6][7][8] The photovoltaic performance was based on optimization with tuning of the electronic structure, band gap, and the effective mass related to the carrier mobility. For example, the incorporation of an alkali metal, [9][10][11][12] organic cation, 13,14 transition metal, [15][16][17][18][19][20][21][22][23] tin, 24,25 and halogen ion, 26,27 improved the photovoltaic performance based on the surface modification, and promotion of the crystal nucleation and growth in the perovskite layer. The perovskite solar cells had many problems to solve regarding the long-term stability of the photovoltaic performance for practical use of the photovoltaic devices.…”

Crystal structures of perovskite halide compounds used for solar cells

“…However, the t-and µ-factors are a simple and helpful guideline to estimate the structural stability of the perovskite halides, and a new tolerance factor was also pro-posed [150]. First-principles calculations based on density functional theory also represent a powerful method to predict the stability and properties of the crystals and doped clusters [151][152][153][154].…”