Accessing the Conduction Band Dispersion in CH₃NH₃PbI₃ Single Crystals

The conduction band dispersion in methylammonium lead iodide (CH₃NH₃PbI₃) was studied by both angle-resolved two-photon photoelectron spectroscopy (AR-2PPE) with low photon intensity (∼0.0125 nJ/pulse) and angle-resolved low-energy inverse photoelectron spectroscopy (AR-LEIPS). Clear energy dispersion of the conduction band along the Γ-M direction was first observed by these independent methods under different temperatures, and the dispersion was found to be consistent with band calculation under the cubic phase. The effective mass of the electrons at the Γ point was estimated to be (0.20 ± 0.05)m₀ at the temperature of 90 K. The observed conduction band energy was different between the AR-LEIPS and AR-2PPE, which was ascribed to the electronic-correlation-dependent difference of initial and final states probing processes. The present results also indicate that the surface structure in CH₃NH₃PbI₃ provides the cubic-dominated electronic property even at lower temperatures.