Leveraging Low-Energy Structural Thermodynamics in Halide Perovskites

Metal halide perovskites (MHPs) combine extraordinary optoelectronic properties with chemical and mechanical properties not found in their semiconductor counterparts. For instance, they exhibit optoelectronic properties on par with single-crystalline gallium arsenide yet exhibit near-zero formation energies. The small lattice energy of MHPs means they undergo a rich diversity of polymorphism near standard conditions similar to organic materials. MHPs also demonstrate ionic transport as high as state-of-the-art battery electrodes. The most widespread applications for metal halide perovskites (e.g. photovoltaics and solid-state lighting) typically view low formation energies, polymorphism, and high ion transport as a nuisance that should be eliminated. Here, we put these properties into perspective by comparing them to other technologically relevant semiconductors in order to highlight how unique this combination of properties is for semiconductors and to illustrate ways to leverage these properties in emerging applications

Sensitivity-Enhanced 207Pb Solid-State NMR Spectroscopy for the Rapid, Non-Destructive Characterization of Organolead Halide Perovskites

Organolead halide and mixed halide perovskites (CH3NH3PbX3, CH3NH3PbX3–nYn, X and Y = Cl–, Br– or I–), are promising materials for photovoltaics and optoelectronic devices. 207Pb solid-state NMR spectroscopy has previously been applied to characterize phase segregation and halide ion speciation in mixed halide perovskites. However, NMR spectroscopy is an insensitive technique that often requires large sample volumes and long signal averaging periods. This is especially true for mixed halide perovskites, which give rise to extremely broad 207Pb solid-state NMR spectra. Here, we quantitatively compare the sensitivity of the various solid-state NMR techniques on pure and mixed halide organolead perovskites and demonstrate that both fast MAS and DNP can provide substantial gains in NMR sensitivity for these materials. With fast MAS and proton detection, high signal-to-noise ratio two-dimensional (2D) 207Pb-1H heteronuclear correlation (HETCOR) NMR spectra can be acquired in less than half an hour from only ca. 5 µL of perovskite material. Modest relayed DNP enhancements on the order of 1 to 20 were obtained for perovskites. The cryogenic temperatures (110 K) used for DNP experiments also provide a significant boost in sensitivity. Consequently, it was possible to obtain the 207Pb solid-state NMR spectrum of a 300 nm thick model thin film of CH3NH3PbI3 in 34 hours by performing solid-state NMR experiments with a sample temperature of 110 K. This result demonstrates the possibility of using NMR spectroscopy for characterization of perovskite thin films

Surface Chemistry of Ternary Nanocrystals: Engineering the Deposition of Conductive NaBiS2 Films

The ability to engineer the surface chemistry of complex ternary nanocrystals is critical to their successful application in photovoltaic, thermoelectric, and other energy conversion devices. For many years, several studies have shed light into the surface chemistry of unary and binary semiconductor nanocrystals, as well as their surface modification with monodentate and multidentate ligands in a variety of applications. In contrast, our understanding of the surface chemistry and ligand modification of ternary and other complex multinary nanocrystals remains relatively limited. Recently, our group reported the synthesis of colloidal NaBiS2 semiconductor nanocrystals with sizes tunable between 2–60 nm, and a light absorption edge of ca. 1.4 eV. Here, we use a combination of infrared and nuclear magnetic resonance spectroscopies to show that the as-made NaBiS2 nanocrystals are capped by oleylamine and neodecanoate ligands. We investigate biphasic liquid-liquid exchange as a means to replace these native ligands with either carboxylate-terminated lipoic acid or with small iodide ligands, leading in both cases to solubility in polar solvents—such as methanol, water, and dimethylformamide. We also investigate a layer-by-layer, biphasic solid-liquid exchange approach to prepare films of NaBiS2 nanocrystals capped with halide ligands—iodide, bromide, chloride. Upon exchange and removal of the native ligands, we show that the resistance of NaBiS2 nanocrystal films greatly decreases, with their measured conductivity being comparable to that of films made of isostructural PbS nanocrystals, which have been used in solar cells. Lastly, we report the first solar cell device made of NaBiS2 nanocrystal films with a limited power conversion efficiency (PCE) of 0.07. Further nanostructuring and ligand optimization may enable the preparation of much more efficient energy conversion devices based on NaBiS2 as well as other non-toxic and Earth-abundant, biocompatible multinary semiconductors

Synthetic Control of the Photoluminescence Stability of Organolead Halide Perovskites

An optimized synthetic procedure for preparing photostable nanocrystalline methylammonium lead halide materials is reported. The procedure was developed by adjusting the lead halide to methylammonium/octylammonium halide precursor ratio. At a high precursor ratio (1:3), a blue-shifted photoinduced luminescence peak is measured at 642 nm for CH3NH3PbI3 with 0.01 to 12 mJ pulsed-laser irradiation. The appearance of this peak is reversible over 300 min upon blocking the irradiation. In order to determine if the peak is the result of a phase change, in situ x-ray diffraction measurements were performed. No phase change was measured with an irradiance that causes the appearance of the photoinduced luminescence peak. Luminescence microscpectroscopy measurements showed that the use of a lower precursor ratio (1:1.5) produces CH3NH3PbI3 and CH3NH3PbBr3 perovskites that are stable over 4 min of illumination. Given the lack of a measured phase change, and the dependence on the precursor ratio, the photoinduced luminesce peak may derive from surface trap states. The enhanced photostability of the resulting perovskite nanocrystals produced with the optimized synthetic procedure supports their use in stable optoelectronic devices