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All Publications

  • Expanded Analogs of Three-Dimensional Lead-Halide Hybrid Perovskites. Angewandte Chemie (International ed. in English) Umeyama, D., Leppert, L., Connor, B., Manumpil, M. A., Neaton, J., Karunadasa, H. 2020


    Replacing the Pb-X octahedral building unit of A I PbX 3 perovskites (X = halide) with a pair of edge-sharing Pb-X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report eight members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrizinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the expanded lattice's bandgap. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with A II = pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the bandgap transition of A II Pb 2 X 6 . The organic-molecule-based conduction band and the inorganic-ion-based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.

    View details for DOI 10.1002/anie.202005012

    View details for PubMedID 32649785

  • A pencil-and-paper method for elucidating halide double perovskite band structures CHEMICAL SCIENCE Slavney, A. H., Connor, B. A., Leppert, L., Karunadasa, H. 2019; 10 (48): 11041–53

    View details for DOI 10.1039/c9sc03219c

    View details for Web of Science ID 000502319900006

  • Understanding and controlling white-light emission from halide perovskites Smith, M., Connor, B., Crace, E., Lindquist, K., Karunadasa, H. AMER CHEMICAL SOC. 2019
  • Tuning the bandgaps of halide double perovskites Slayney, A., Connor, B., Leppert, L., Neaton, J. B., Karunadasa, H. AMER CHEMICAL SOC. 2019
  • Dimensional reduction of halide double perovskites Connor, B., Leppert, L., Smith, M., Neaton, J. B., Karunadasa, H. AMER CHEMICAL SOC. 2019
  • Teaching halide double perovskites to absorb sunlight Slavney, A., Connor, B., Leppert, L., Neaton, J. B., Karunadasa, H. AMER CHEMICAL SOC. 2019
  • Tuning the Luminescence of Layered Halide Perovskites. Chemical reviews Smith, M. D., Connor, B. A., Karunadasa, H. I. 2019


    Layered halide perovskites offer a versatile platform for manipulating light through synthetic design. Although most layered perovskites absorb strongly in the ultraviolet (UV) or near-UV region, their emission can range from the UV to the infrared region of the electromagnetic spectrum. This emission can be very narrow, displaying high color purity, or it can be extremely broad, spanning the entire visible spectrum and providing high color rendition (or accurately reproducing illuminated colors). The origin of the photoluminescence can vary enormously. Strongly correlated electron-hole pairs, permanent lattice defects, transient light-induced defects, and ligand-field transitions in the inorganic layers and molecular chromophores in the organic layers can be involved in the emission mechanism. In this review, we highlight the different types of photoluminescence that may be attained from layered halide perovskites, with an emphasis on how the emission may be systematically tuned through changes to the bulk crystalline lattice: changes in composition, structure, and dimensionality.

    View details for PubMedID 30689364

  • A pencil-and-paper method for elucidating halide double perovskite band structures. Chemical science Slavney, A. H., Connor, B. A., Leppert, L., Karunadasa, H. I. 2019; 10 (48): 11041–53


    Halide double perovskites are an important emerging alternative to lead-halide perovskites in a variety of optoelectronic applications. Compared to ABX3 single perovskites (A = monovalent cation, X = halide), A2BB'X6 double perovskites exhibit a wider array of compositions and electronic structures, promising finer control over physical and electronic properties through synthetic design. However, a clear understanding of how chemical composition dictates the electronic structures of this large family of materials is still lacking. Herein, we develop a qualitative Linear Combination of Atomic Orbitals (LCAO) model that describes the full range of band structures for double perovskites. Our simple model allows for a direct connection between the inherently local bonding between atoms in the double perovskite and the resulting delocalized bands of the solid. In particular, we show how bands in halide double perovskites originate from the molecular orbitals of metal-hexahalide coordination complexes and describe how these molecular orbitals vary within a band. Our results provide both an enhanced understanding of known perovskite compositions and predictive power for identifying new compositions with targeted properties. We present a table, which permits the position of the conduction band minimum and valence band maximum in most double perovskites to be immediately determined from the frontier atomic orbitals of the B-site metals. Using purely qualitative arguments based on orbital symmetries and their relative energies, the direct/indirect nature of the bandgap of almost all halide double perovskites can thus be correctly predicted. We hope that this theory provides an intuitive understanding of halide double perovskite band structures and enables lessons from molecular chemistry to be applied to these extended solids.

    View details for DOI 10.1039/c9sc03219c

    View details for PubMedID 32190254

    View details for PubMedCentralID PMC7066864

  • Layered Halide Double Perovskites: Dimensional Reduction of Cs2AgBiBr6 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Connor, B. A., Leppert, L., Smith, M. D., Neaton, J. B., Karunadasa, H. I. 2018; 140 (15): 5235–40


    We investigate the consequences of dimensional confinement on halide double perovskites by synthesizing two-dimensional analogues of the recently reported three-dimensional double perovskite Cs2AgBiBr6. The layered perovskites (BA)4AgBiBr8 (1) and (BA)2CsAgBiBr7 (2) (BA = CH3(CH2)3NH3+) feature metal-halide sheets of mono and bilayer thickness, respectively, where the ordered double-perovskite lattice is partitioned by organic cations. Electronic structure calculations indicate that the indirect bandgap of Cs2AgBiBr6 becomes direct when the infinitely thick inorganic lattice is reduced to monolayer thickness. Calculations on model systems allow us to separate the effects of dimensional reduction from those of the accompanying structural distortions in the inorganic sublattice. Detailed optical characterization shows that the photophysical properties of 1 and 2 are markedly different than those of their well-studied lead-halide analogs. Hybrid layered derivatives of double perovskites substantially expand on the substitutional flexibility of halide perovskites to encompass greater compositional and electronic diversity.

    View details for PubMedID 29575889

  • Charge Carrier Dynamics in Cs2AgBiBr6 Double Perovskite JOURNAL OF PHYSICAL CHEMISTRY C Bartesaghi, D., Slavney, A. H., Gelvez-Rueda, M. C., Connor, B. A., Grozema, F. C., Karunadasa, H. I., Savenije, T. J. 2018; 122 (9): 4809–16


    Double perovskites, comprising two different cations, are potential nontoxic alternatives to lead halide perovskites. Here, we characterized thin films and crystals of Cs2AgBiBr6 by time-resolved microwave conductance (TRMC), which probes formation and decay of mobile charges upon pulsed irradiation. Optical excitation of films results in the formation of charges with a yield times mobility product, φΣμ > 1 cm2/Vs. On excitation of millimeter-sized crystals, the TRMC signals show, apart from a fast decay, a long-lived tail. Interestingly, this tail is dominant when exciting close to the bandgap, implying the presence of mobile charges with microsecond lifetimes. From the temperature and intensity dependence of the TRMC signals, we deduce a shallow trap state density of around 1016/cm3 in the bulk of the crystal. Despite this high concentration, trap-assisted recombination of charges in the bulk appears to be slow, which is promising for photovoltaic applications.

    View details for PubMedID 29545908