Aryeh Gold-Parker

Defect-Induced Band-Edge Reconstruction of a Bismuth-Halide Double Perovskite for Visible-Light Absorption

Halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX3 (A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs2AgBiBr6 (1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1s bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyed perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH3NH3)PbI3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1s band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX3 absorbers.

Band Gap Tuning via Lattice Contraction and Octahedral Tilting in Perovskite Materials for Photovoltaics

Tin and lead iodide perovskite semiconductors of the composition AMX3, where M is a metal and X is a halide, are leading candidates for high efficiency low cost tandem photovoltaics, in part because they have band gaps that can be tuned over a wide range by compositional substitution. We experimentally identify two competing mechanisms through which the A-site cation influences the band gap of 3D metal halide perovskites. Using a smaller A-site cation can distort the perovskite lattice in two distinct ways: by tilting the MX6 octahedra or by simply contracting the lattice isotropically. The former effect tends to raise the band gap, while the latter tends to decrease it. Lead iodide perovskites show an increase in band gap upon partial substitution of the larger formamidinium with the smaller cesium, due to octahedral tilting. Perovskites based on tin, which is slightly smaller than lead, show the opposite trend: they show no octahedral tilting upon Cs-substitution but only a contraction of the lattice, leading to progressive reduction of the band gap. We outline a strategy to systematically tune the band gap and valence and conduction band positions of metal halide perovskites through control of the cation composition. Using this strategy, we demonstrate solar cells that harvest light in the infrared up to 1040 nm, reaching a stabilized power conversion efficiency of 17.8%, showing promise for improvements of the bottom cell of all-perovskite tandem solar cells. The mechanisms of cation-based band gap tuning we describe are broadly applicable to 3D metal halide perovskites and will be useful in further development of perovskite semiconductors for optoelectronic applications.

Compositional and orientational control in metal halide perovskites of reduced dimensionality

Reduced-dimensional metal halide perovskites (RDPs) have attracted significant attention in recent years due to their promising light harvesting and emissive properties. We sought to increase the systematic understanding of how RDPs are formed. Here we report that layered intermediate complexes formed with the solvent provide a scaffold that facilitates the nucleation and growth of RDPs during annealing, as observed via in situ X-ray scattering. Transient absorption spectroscopy of RDP single crystals and films enables the identification of the distribution of quantum well thicknesses. These insights allow us to develop a kinetic model of RDP formation that accounts for the experimentally observed size distribution of wells. RDPs exhibit a thickness distribution (with sizes that extend above n = 5) determined largely by the stoichiometric proportion between the intercalating cation and solvent complexes. The results indicate a means to control the distribution, composition and orientation of RDPs via the selection of the intercalating cation, the solvent and the deposition technique.A systematic analysis is performed to reveal how deposition conditions and the use of cations and solvents affect the composition and orientation of 2D and quasi-2D metal halide perovskites in thin films.

Transformation from crystalline precursor to perovskite in PbCl 2 -derived MAPbI 3

Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI3) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl2 + 3MAI) (MA = CH3NH3). The as-spun film consists of crystalline MA2PbI3Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. This enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.The existence of a crystalline precursor is key to perovskite film formation, but the precise chemistry of the precursor and its transformation into perovskite are poorly understood. Here, the authors identify the crystal structure and conversion chemistry of the precursor for PbCl2-derived methylammonium lead iodide perovskites.