title: Hybrid germanium iodide perovskite semiconductors: active lone pairs, structural distortions, direct and indirect energy gaps, and strong nonlinear optical properties.
abstract: The synthesis and properties of the hybrid organic/inorganic germanium perovskite compounds, AGeI3, are reported (A = Cs, organic cation). The systematic study of this reaction system led to the isolation of 6 new hybrid semiconductors. Using CsGeI3 (1) as the prototype compound, we have prepared methylammonium, CH3NH3GeI3 (2), formamidinium, HC(NH2)2GeI3 (3), acetamidinium, CH3C(NH2)2GeI3 (4), guanidinium, C(NH2)3GeI3 (5), trimethylammonium, (CH3)3NHGeI3 (6), and isopropylammonium, (CH3)2C(H)NH3GeI3 (7) analogues. The crystal structures of the compounds are classified based on their dimensionality with 1–4 forming 3D perovskite frameworks and 5–7 1D infinite chains. Compounds 1–7, with the exception of compounds 5 (centrosymmetric) and 7 (nonpolar acentric), crystallize in polar space groups. The 3D compounds have direct band gaps of 1.6 eV (1), 1.9 eV (2), 2.2 eV (3), and 2.5 eV (4), while the 1D compounds have indirect band gaps of 2.7 eV (5), 2.5 eV (6), and 2.8 eV (7). Herein, we report on the second harmonic generation (SHG) properties of the compounds, which display remarkably strong, type I phase-matchable SHG response with high laser-induced damage thresholds (up to ∼3 GW/cm(2)). The second-order nonlinear susceptibility, χS(2), was determined to be 125.3 ± 10.5 pm/V (1), (161.0 ± 14.5) pm/V (2), 143.0 ± 13.5 pm/V (3), and 57.2 ± 5.5 pm/V (4). First-principles density functional theory electronic structure calculations indicate that the large SHG response is attributed to the high density of states in the valence band due to sp-hybridization of the Ge and I orbitals, a consequence of the lone pair activation.
authors.affiliation: †Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
authors.forename: Constantinos C
authors.initials: CC
authors.lastname: Stoumpos
authors.affiliation: ‡Department of Physics and Astronomy, Northwestern University, Evanston, Illinois 60208, United States.
authors.forename: Laszlo
authors.initials: L
authors.lastname: Frazer
authors.affiliation: §Department of Physics, Applied Physics and Astronomy, State University of New York (SUNY) at Binghamton, Binghamton, New York 13902, United States.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Clark
authors.affiliation: §Department of Physics, Applied Physics and Astronomy, State University of New York (SUNY) at Binghamton, Binghamton, New York 13902, United States.|∥Department of Physics and Energy Harvest-Storage Research Center, University of Ulsan, Ulsan 680-749, South Korea.
authors.forename: Yong Soo
authors.initials: YS
authors.lastname: Kim
authors.affiliation: ‡Department of Physics and Astronomy, Northwestern University, Evanston, Illinois 60208, United States.|∥Department of Physics and Energy Harvest-Storage Research Center, University of Ulsan, Ulsan 680-749, South Korea.
authors.forename: Sonny H
authors.initials: SH
authors.lastname: Rhim
authors.affiliation: ‡Department of Physics and Astronomy, Northwestern University, Evanston, Illinois 60208, United States.
authors.forename: Arthur J
authors.initials: AJ
authors.lastname: Freeman
authors.affiliation: ‡Department of Physics and Astronomy, Northwestern University, Evanston, Illinois 60208, United States.
authors.forename: John B
authors.initials: JB
authors.lastname: Ketterson
authors.affiliation: §Department of Physics, Applied Physics and Astronomy, State University of New York (SUNY) at Binghamton, Binghamton, New York 13902, United States.
authors.forename: Joon I
authors.initials: JI
authors.lastname: Jang
authors.affiliation: †Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
authors.forename: Mercouri G
authors.initials: MG
authors.lastname: Kanatzidis