All of the cations currently used in perovskite solar cells abide by the tolerance factor for incorporation into the lattice. We show that the small and oxidation-stable rubidium cation (Rb + ) can be embedded into a “cation cascade” to create perovskite materials with excellent material properties. We achieved stabilized efficiencies of up to 21.6% (average value, 20.2%) on small areas (and a stabilized 19.0% on a cell 0.5 square centimeters in area) as well as an electroluminescence of 3.8%. The open-circuit voltage of 1.24 volts at a band gap of 1.63 electron volts leads to a loss in potential of 0.39 volts, versus 0.4 volts for commercial silicon cells. Polymer-coated cells maintained 95% of their initial performance at 85°C for 500 hours under full illumination and maximum power point tracking.

https://science.sciencemag.org/content/sci/early/2016/09/28/science.aah5557.full.pdf

Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance

Although known since the late 19th century, organic–inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic–inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design

Organometal halide perovskites exhibit large bulk crystal domain sizes, rare traps, excellent mobilities and carriers that are free at room temperature-properties that support their excellent performance in charge-separating devices. In devices that rely on the forward injection of electrons and holes, such as light-emitting diodes (LEDs), excellent mobilities contribute to the efficient capture of non-equilibrium charge carriers by rare non-radiative centres. Moreover, the lack of bound excitons weakens the competition of desired radiative (over undesired non-radiative) recombination. Here we report a perovskite mixed material comprising a series of differently quantum-size-tuned grains that funnels photoexcitations to the lowest-bandgap light-emitter in the mixture. The materials function as charge carrier concentrators, ensuring that radiative recombination successfully outcompetes trapping and hence non-radiative recombination. We use the new material to build devices that exhibit an external quantum efficiency (EQE) of 8.8% and a radiance of 80 W sr-1 m-2. These represent the brightest and most efficient solution-processed near-infrared LEDs to date.

Perovskite energy funnels for efficient light-emitting diodes

Goldschmidt tolerance factor (t) is an empirical index for predicting stable crystal structures of perovskite materials. A t value between 0.8 and 1.0 is favorable for cubic perovskite structure, and larger (>1) or smaller (<0.8) values of tolerance factor usually result in nonperovskite structures. CH(NH2)2PbI3 (FAPbI3) can exist in the perovskite α-phase (black phase) with good photovoltaic properties. However, it has a large tolerance factor and is more stable in the hexagonal δH-phase (yellow phase), with δH-to-α phase-transition temperature higher than room temperature. On the other hand, CsPbI3 is stabilized to an orthorhombic structure (δO-phase) at room temperature due to its small tolerance factor. We find that, by alloying FAPbI3 with CsPbI3, the effective tolerance factor can be tuned, and the stability of the photoactive α-phase of the mixed solid-state perovskite alloys FA1–xCsxPbI3 is enhanced, which is in agreement with our first-principles calculations. Thin films of the FA0.85Cs0.15PbI3 p...

Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys

Rapidly increasing atmospheric CO2 concentrations threaten human society, the natural environment, and the synergy between the two. In order to ameliorate the CO2 problem, carbon capture and conversion techniques have been proposed. Metal–organic framework (MOF)-based materials, a relatively new class of porous materials with unique structural features, high surface areas, chemical tunability and stability, have been extensively studied with respect to their applicability to such techniques. Recently, it has become apparent that the CO2 capture capabilities of MOF-based materials significantly boost their potential toward CO2 conversion. Furthermore, MOF-based materials’ well-defined structures greatly facilitate the understanding of structure–property relationships and their roles in CO2 capture and conversion. In this review, we provide a comprehensive account of significant progress in the design and synthesis of MOF-based materials, including MOFs, MOF composites and MOF derivatives, and their application to carbon capture and conversion. Special emphases on the relationships between CO2 capture capacities of MOF-based materials and their catalytic CO2 conversion performances are discussed.

Carbon capture and conversion using metal–organic frameworks and MOF-based materials

Hybrid organic–inorganic materials that adopt perovskite-like architectures show intriguing order–disorder phase transitions and exciting electronic properties. We extend the classical concept of ionic tolerance factors to this important class of materials and predict the existence of several hitherto undiscovered hybrid perovskite phases.

/pdf/solid-state-principles-applied-to-organic-inorganic-25v15efi8y.pdf

Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog

Goldschmidt's concept of ionic Tolerance Factors was recently shown to be a valuable guideline for the preparation of new compounds within the field of organic–inorganic perovskites. Here, we extend this approach and calculate Tolerance Factors for over 2500 amine–metal–anion permutations of the periodic table. The results suggest the potential existence of more than 600 undiscovered hybrid perovskites including alkaline earth metal and lanthanide based materials.

/pdf/an-extended-tolerance-factor-approach-for-organic-inorganic-3vg0eetu4o.pdf

An extended Tolerance Factor approach for organic–inorganic perovskites

The targeted incorporation of defects into crystalline matter allows for the manipulation of many properties and has led to relevant discoveries for optimized and even novel technological applications of materials. It is therefore exciting to see that defects are now recognized to be similarly useful in tailoring properties of metal-organic frameworks (MOFs). For instance, heterogeneous catalysis crucially depends on the number of active catalytic sites as well as on diffusion limitations. By the incorporation of missing linker and missing node defects into MOFs, both parameters can be accessed, improving the catalytic properties. Furthermore, the creation of defects allows for adding properties such as electronic conductivity, which are inherently absent in the parent MOFs. Herein, progress of the rapidly evolving field of the past two years is overviewed, putting a focus on properties that are altered by the incorporation and even tailoring of defects in MOFs. A brief account is also given on the emerging quantitative understanding of defects and heterogeneity in MOFs based on scale-bridging computational modeling and simulations.

/pdf/defective-metal-organic-frameworks-4c2xma1xor.pdf

Defective Metal-Organic Frameworks.

The discovery of lead-free hybrid double perovskites provides a viable approach in the search for stable and environmentally benign photovoltaic materials as alternatives to lead-containing systems such as MAPbX3 (X = Cl, Br, or I). Following our recent reports of (MA)2KBiCl6 and (MA)2TlBiBr6, we have now synthesized a hybrid double perovskite, (MA)2AgBiBr6, that has a low band gap of 2.02 eV and is relatively stable and nontoxic. Its electronic structure and mechanical and optical properties are investigated with a combination of experimental studies and density functional theory calculations.

Synthesis and Properties of a Lead-Free Hybrid Double Perovskite: (CH3NH3)2AgBiBr6

In a search for lead-free materials that could be used as alternatives to the hybrid perovskites, (MA)PbX3, in photovoltaic applications, we have discovered a hybrid double perovskite, (MA)2KBiCl6, which shows strong similarities to the lead analogues. Spectroscopic measurements and nanoindentation studies are combined with density functional calculations to reveal the properties of this interesting system.

Gregor Kieslich

Papers

Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog

An extended Tolerance Factor approach for organic–inorganic perovskites

Defective Metal-Organic Frameworks.

Synthesis and Properties of a Lead-Free Hybrid Double Perovskite: (CH3NH3)2AgBiBr6

The synthesis, structure and electronic properties of a lead-free hybrid inorganic–organic double perovskite (MA)2KBiCl6 (MA = methylammonium)