Temperature-dependent optical spectra of single-crystal (CH₃NH₃)PbBr₃ cleaved in ultrahigh vacuum

We measure temperature-dependent one-photon and two-photon induced photoluminescence from (CH3NH3)PbBr3 single crystals cleaved in ultrahigh vacuum. An approach is presented to extract absorption spectra from a comparison of both measurements. Cleaved crystals exhibit broad photoluminescence spectra. We identify the direct optical band gap of 2.31 eV. Below 200 K the band gap increases with temperature, and it decreases at elevated temperature, as described by the Bose-Einstein model. An excitonic transition is found 22 meV below the band gap at temperatures <200 K. Defect emission occurs at photon energies <2.16 eV. In addition, we observe a transition at 2.25 eV (2.22 eV) in the orthorhombic (tetragonal and cubic) phase. Below 200 K, the associated exciton binding energy is also 22 meV, and the transition redshifts at higher temperature. The binding energy of the exciton related to the direct band gap, in contrast, decreases in the cubic phase. High-energy emission from free carriers is observed with higher intensity than reported in earlier studies. It disappears after exposing the crystals to air.