title: Simultaneous observation of free and defect-bound excitons in CH3NH3PbI3using four-wave mixing spectroscopy.
abstract: Solar cells incorporating organic-inorganic perovskite, which may be fabricated using low-cost solution-based processing, have witnessed a dramatic rise in efficiencies yet their fundamental photophysical properties are not well understood. The exciton binding energy, central to the charge collection process, has been the subject of considerable controversy due to subtleties in extracting it from conventional linear spectroscopy techniques due to strong broadening tied to disorder. Here we report the simultaneous observation of free and defect-bound excitons in CH3NH3PbI3films using four-wave mixing (FWM) spectroscopy. Due to the high sensitivity of FWM to excitons, tied to their longer coherence decay times than unbound electron- hole pairs, we show that the exciton resonance energies can be directly observed from the nonlinear optical spectra. Our results indicate low-temperature binding energies of 13 meV (29 meV) for the free (defect-bound) exciton, with the 16 meV localization energy for excitons attributed to binding to point defects. Our findings shed light on the wide range of binding energies (2-55 meV) reported in recent years.
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2 Canada.
authors.forename: Samuel A
authors.initials: SA
authors.lastname: March
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2 Canada.
authors.forename: Charlotte
authors.initials: C
authors.lastname: Clegg
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2 Canada.
authors.forename: Drew B
authors.initials: DB
authors.lastname: Riley
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2 Canada.
authors.forename: Daniel
authors.initials: D
authors.lastname: Webber
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2 Canada.
authors.forename: Ian G
authors.initials: IG
authors.lastname: Hill
authors.affiliation: Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 4R2 Canada.
authors.forename: Kimberley C
authors.initials: KC
authors.lastname: Hall