Halide Perovskites Breathe Too: The Iodide-Iodine Equilibrium and Self-Doping in Cs2SnI6.

The response of an oxide crystal to the atmosphere can be personified as breathing-a dynamic equilibrium between O2 gas and O2- anions in the solid. We characterize the analogous defect reaction in an iodide double-perovskite semiconductor, Cs2SnI6. Here, I2 gas is released from the crystal at room temperature, forming iodine vacancies. The iodine vacancy defect is a shallow electron donor and is therefore ionized at room temperature; thus, the loss of I2 is accompanied by spontaneous n-type self-doping. Conversely, at high I2 pressures, I2 gas is resorbed by the perovskite, consuming excess electrons as I2 is converted to 2I-. Halide mobility and irreversible halide loss or exchange reactions have been studied extensively in halide perovskites. However, the reversible exchange equilibrium between iodide and iodine [2I-(s) ↔ I2(g) + 2e-] described here has often been overlooked in prior studies, though it is likely general to halide perovskites and operative near room temperature, even in the dark. An analysis of the 2I-(s)/I2(g) equilibrium thermodynamics and related transport kinetics in single crystals of Cs2SnI6 therefore provides insight toward achieving stable composition and electronic properties in the large family of iodide perovskite semiconductors.

Understanding the evolution of double perovskite band structure upon dimensional reduction.

Recent investigations into the effects of dimensional reduction on halide double perovskites have revealed an intriguing change in band structure when the three-dimensional (3D) perovskite is reduced to a two-dimensional (2D) perovskite with inorganic sheets of monolayer thickness (n = 1). The indirect bandgap of 3D Cs2AgBiBr6 becomes direct in the n = 1 perovskite whereas the direct bandgap of 3D Cs2AgTlBr6 becomes indirect at the n = 1 limit. Here, we apply a linear combination of atomic orbitals approach to uncover the orbital basis for this bandgap symmetry transition with dimensional reduction. We adapt our previously established method for predicting band structures of 3D double perovskites for application to their 2D congeners, emphasizing new considerations required for the 2D lattice. In particular, we consider the inequivalence of the terminal and bridging halides and the consequences of applying translational symmetry only along two dimensions. The valence and conduction bands of the layered perovskites can be derived from symmetry adapted linear combinations of halide p orbitals propagated across the 2D lattice. The dispersion of each band is then determined by the bonding and antibonding interactions of the metal and halide orbitals, thus affording predictions of the essential features of the band structure. We demonstrate this analysis for 2D Ag-Bi and Ag-Tl perovskites with sheets of mono- and bilayer thickness, establishing a detailed understanding of their band structures, which enables us to identify the key factors that drive the bandgap symmetry transitions observed at the n = 1 limit. Importantly, these insights also allow us to make the general prediction that direct → indirect or indirect → direct bandgap transitions in the monolayer limit are most likely in double perovskite compositions that involve participation of metal d orbitals at the band edges or that have no metal-orbital contributions to the valence band, laying the groundwork for the targeted realization of this phenomenon.

Generalizable Synthesis of Highly Fluorinated Ionic Liquids.

The unique chemistry of fluorocarbons (in particular, their weak intermolecular interactions and high degree of intrinsic free volume) makes them promising building blocks for ionic liquids with high gas capacities. Here, we report a generalizable method for the synthesis of fluorinated ionic liquids, which relies on the evolution of gaseous byproducts to drive product formation. This synthetic strategy overcomes solubility challenges that can hinder the synthesis of highly fluorinated ionic liquids via conventional methods and enables a systematic investigation of the effect of fluorination on ionic liquid viscosity and gas solubility.

Tuning Defects in a Halide Double Perovskite with Pressure.

Dopant defects in semiconductors can trap charge carriers or ionize to produce charge carriers─playing a critical role in electronic transport. Halide perovskites are a technologically important semiconductor family with a large pressure response. Yet, to our knowledge, the effect of high pressures on defects in halide perovskites has not been experimentally investigated. Here, we study the structural, optical, and electronic consequences of compressing the small-bandgap double perovskites Cs2AgTlX6 (X = Cl or Br) up to 56 GPa. Mild compression to 1.7 GPa increases the conductivity of Cs2AgTlBr6 by ca. 1 order of magnitude and decreases its bandgap from 0.94 to 0.7 eV. Subsequent compression yields complex optoelectronic behavior: the bandgap varies by 1.2 eV and conductivity ranges by a factor of 104. These conductivity changes cannot be explained by the evolving bandgap. Instead, they can be understood as tuning of the bromine vacancy defect with pressure─varying between a delocalized shallow defect state with a small ionization energy and a localized deep defect state with a large ionization energy. Activation energy measurements reveal that the shallow-to-deep defect transition occurs near 1.5 GPa, well before the cubic-to-tetragonal phase transition. An analysis of the orbital interactions in Cs2AgTlBr6 illustrates how the bromine vacancy weakens the adjacent Tl s-Br p antibonding interaction, driving the shallow-to-deep defect transition. Our orbital analysis leads us to propose that halogen vacancies are most likely to be shallow donors in halide double perovskites that have a conduction band derived from the octahedral metal's s orbitals.

Designing Glass and Crystalline Phases of Metal-Bis(acetamide) Networks to Promote High Optical Contrast.

Owing to their high tunability and predictable structures, metal-organic materials offer a powerful platform to study glass formation and crystallization processes and to design glasses with unique properties. Here, we report a novel series of glass-forming metal-ethylenebis(acetamide) networks that undergo reversible glass and crystallization transitions below 200 °C. The glass-transition temperatures, crystallization kinetics, and glass stability of these materials are readily tunable, either by synthetic modification or by liquid-phase blending, to form binary glasses. Pair distribution function (PDF) analysis reveals extended structural correlations in both single and binary metal-bis(acetamide) glasses and highlights the important role of metal-metal correlations during structural evolution across glass-crystal transitions. Notably, the glass and crystalline phases of a Co-ethylenebis(acetamide) binary network feature a large reflectivity contrast ratio of 4.8 that results from changes in the local coordination environment around Co centers. These results provide new insights into glass-crystal transitions in metal-organic materials and have exciting implications for optical switching, rewritable data storage, and functional glass ceramics.

Liquid and Glass Phases of an Alkylguanidinium Sulfonate Hydrogen-Bonded Organic Framework.

Glassy phases of framework materials feature unique and tunable properties that are advantageous for gas separation membranes, solid electrolytes, and phase-change memory applications. Here, we report a new guanidinium organosulfonate hydrogen-bonded organic framework (HOF) that melts and vitrifies below 100 °C. In this low-temperature regime, non-covalent interactions between guest molecules and the porous framework become a dominant contributor to the overall stability of the structure, resulting in guest-dependent melting, glass, and recrystallization transitions. Through simulations and X-ray scattering, we show that the local structures of the amorphous liquid and glass phases resemble those of the parent crystalline framework.

Colossal barocaloric effects with ultralow hysteresis in two-dimensional metal-halide perovskites.

Pressure-induced thermal changes in solids-barocaloric effects-can be used to drive cooling cycles that offer a promising alternative to traditional vapor-compression technologies. Efficient barocaloric cooling requires materials that undergo reversible phase transitions with large entropy changes, high sensitivity to hydrostatic pressure, and minimal hysteresis, the combination of which has been challenging to achieve in existing barocaloric materials. Here, we report a new mechanism for achieving colossal barocaloric effects that leverages the large volume and conformational entropy changes of hydrocarbon order-disorder transitions within the organic bilayers of select two-dimensional metal-halide perovskites. Significantly, we show how the confined nature of these order-disorder phase transitions and the synthetic tunability of layered perovskites can be leveraged to reduce phase transition hysteresis through careful control over the inorganic-organic interface. The combination of ultralow hysteresis and high pressure sensitivity leads to colossal reversible isothermal entropy changes (>200 J kg-1 K-1) at record-low pressures (<300 bar).

Understanding Relationships between Free Volume and Oxygen Absorption in Ionic Liquids.

Understanding the factors that govern gas absorption in ionic liquids is critical to the development of high-capacity solvents for catalysis, electrochemistry, and gas separations. Here, we report experimental probes of liquid structure that provide insights into how free volume impacts the O2 absorption properties of ionic liquids. Specifically, we establish that isothermal compressibility─measured rapidly and accurately through small-angle X-ray scattering─reports on the size distribution of transient voids within a representative series of ionic liquids and is correlated with O2 absorption capacity. Additionally, O2 absorption capacities are correlated with thermal expansion coefficients, reflecting the beneficial effect of weak intermolecular interactions in ionic liquids on free volume and gas absorption capacity. Molecular dynamics simulations show that the void size distribution─in particular, the probability of forming larger voids within an ionic liquid─has a greater impact on O2 absorption than the total free volume. These results establish relationships between the ionic liquid structure and gas absorption properties that offer design strategies for ionic liquids with high gas solubilities.

Doubling the Stakes: The Promise of Halide Double Perovskites.

When the stakes are doubled in a wager, a player must correctly place two consecutive bets to win, but the payout is larger. Similarly, two B sites in combination dictate the properties of A2 BB'X6 (A=monocation, X=halide) double perovskites. Correctly picking two B sites is more challenging than picking just one, as in the AI BII X3 single perovskites, but the options are greater and, we believe, the rewards are higher when the stakes are doubled. In this Minireview, we emphasize fundamental aspects of halide double perovskites to provide a foundation for interested readers to explore this extraordinary class of materials. In particular, we highlight the differences and similarities between double and single perovskites and describe how the double perovskite structure potentially offers greater control over photophysical properties.

Network-Forming Liquids from Metal-Bis(acetamide) Frameworks with Low Melting Temperatures.

Molten phases of metal-organic networks offer exciting opportunities for using coordination chemistry principles to access liquids and glasses with unique and tunable structures and properties. Here, we discuss general thermodynamic strategies to provide an increased enthalpic and entropic driving force for reversible, low-temperature melting transitions in extended coordination solids and illustrate this approach through a systematic study of a series of bis(acetamide)-based networks with record-low melting temperatures. The low melting temperatures of these compounds are the result of weak coordination bonds, conformationally flexible bridging ligands, and weak electrostatic interactions between spatially separated cations and anions, which collectively reduce the enthalpy and increase the entropy of fusion. Through a combination of crystallography, spectroscopy, and calorimetry, enthalpic trends are found to be dictated by the strength of coordination bonds and hydrogen bonds within each compound, while entropic trends are strongly influenced by the degree to which residual motion and positional disorder are restricted in the crystalline state. Extended X-ray absorption fine structure (EXAFS) and pair distribution function (PDF) analysis of Co(bba)3[CoCl4] [bba = N,N'-1,4-butylenebis(acetamide)], which features a record-low melting temperature for a three-dimensional metal-organic network of 124 °C, provide direct evidence of metal-ligand coordination in the liquid phase, as well as intermediate- and extended-range order that support its network-forming nature. In addition, rheological measurements are used to rationalize differences in glass-forming ability and relaxation dynamics. These results provide new insights into the structural and chemical factors that influence the thermodynamics of melting transitions of extended coordination solids, as well as the structure and properties of coordination network-forming liquids.

Revealing Local Disorder in a Silver-Bismuth Halide Perovskite upon Compression.

The halide double perovskite Cs2AgBiBr6 has emerged as a promising nontoxic alternative to the lead halide perovskites APbX3 (A = organic cation or Cs; X = I or Br). Here, we perform high-pressure synchrotron X-ray total scattering on Cs2AgBiBr6 and discover local disorder that is hidden from conventional Bragg analysis. While our powder diffraction data show that the average structure remains cubic up to 2.1 GPa, analysis of the X-ray pair distribution function reveals that the local structure is better described by a monoclinic space group, with significant distortion within the Ag-Br and Bi-Br octahedra and off-centering of the Cs atoms. By tracking the distribution of interatomic Cs-Br distances, we find that the local disorder is enhanced upon compression, and we corroborate these results with molecular dynamics simulations. The observed local disorder affords new understanding of this promising material and potentially offers a new parameter to tune in halide perovskite lattices.

Reactivity of NO2 with Porous and Conductive Copper Azobispyridine Metallopolymers.

We report the reactivity of copper azobispyridine (abpy) metallopolymers with nitrogen dioxide (NO2). The porous and conductive [Cu(abpy)]n mixed-valence metallopolymers undergo a redox reaction with NO2, resulting in the disproportionation of NO2 gas. Solid- and gas-phase vibrational spectroscopy and X-ray analysis of the reaction products of the NO2-dosed metallopolymer show evidence of nitrate ions and nitric oxide gas. Exposure to NO2 results in complete loss of porosity and a decrease in the room-temperature conductivity of the metallopolymer by four orders of magnitude with the loss of mixed-valence character. Notably, the porous and conductive [Cu(abpy)]n metallopolymers can be reformed by reducing the Cu-nitrate species.

Tuning the bandgap of Cs2AgBiBr6 through dilute tin alloying.

The promise of lead halide hybrid perovskites for optoelectronic applications makes finding less-toxic alternatives a priority. The double perovskite Cs2AgBiBr6 (1) represents one such alternative, offering long carrier lifetimes and greater stability under ambient conditions. However, the large and indirect 1.95 eV bandgap hinders its potential as a solar absorber. Here we report that alloying crystals of 1 with up to 1 atom% Sn results in a bandgap reduction of up to ca. 0.5 eV while maintaining low toxicity. Crystals can be alloyed with up to 1 atom% Sn and the predominant substitution pathway appears to be a ∼2 : 1 substitution of Sn2+ and Sn4+ for Ag+ and Bi3+, respectively, with Ag+ vacancies providing charge compensation. Spincoated films of 1 accommodate a higher Sn loading, up to 4 atom% Sn, where we see mostly Sn2+ substitution for both Ag+ and Bi3+. Density functional theory (DFT) calculations ascribe the bandgap redshift to the introduction of Sn impurity bands below the conduction band minimum of the host lattice. Using optical absorption spectroscopy, photothermal deflection spectroscopy, X-ray absorption spectroscopy, 119Sn NMR, redox titration, single-crystal and powder X-ray diffraction, multiple elemental analysis and imaging techniques, and DFT calculations, we provide a detailed analysis of the Sn content and oxidation state, dominant substitution sites, and charge-compensating defects in Sn-alloyed Cs2AgBiBr6 (1:Sn) crystals and films. An understanding of heterovalent alloying in halide double perovskites opens the door to a wider breadth of potential alloying agents for manipulating their band structures in a predictable manner.

A pencil-and-paper method for elucidating halide double perovskite band structures.

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.

Small-Band-Gap Halide Double Perovskites.

Despite their compositional versatility, most halide double perovskites feature large band gaps. Herein, we describe a strategy for achieving small band gaps in this family of materials. The new double perovskites Cs2 AgTlX6 (X=Cl (1) and Br (2)) have direct band gaps of 2.0 and 0.95 eV, respectively, which are approximately 1 eV lower than those of analogous perovskites. To our knowledge, compound 2 displays the lowest band gap for any known halide perovskite. Unlike in AI BII X3 perovskites, the band-gap transition in AI2 BB'X6 double perovskites can show substantial metal-to-metal charge-transfer character. This band-edge orbital composition is used to achieve small band gaps through the selection of energetically aligned B- and B'-site metal frontier orbitals. Calculations reveal a shallow, symmetry-forbidden region at the band edges for 1, which results in long (µs) microwave conductivity lifetimes. We further describe a facile self-doping reaction in 2 through Br2 loss at ambient conditions.

Charge Carrier Dynamics in Cs2AgBiBr6 Double Perovskite.

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.

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 1's 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 1's band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX3 absorbers.

Chemical Approaches to Addressing the Instability and Toxicity of Lead-Halide Perovskite Absorbers.

The impressive rise in efficiencies of solar cells employing the three-dimensional (3D) lead-iodide perovskite absorbers APbI3 (A = monovalent cation) has generated intense excitement. Although these perovskites have remarkable properties as solar-cell absorbers, their potential commercialization now requires a greater focus on the materials' inherent shortcomings and environmental impact. This creates a challenge and an opportunity for synthetic chemists to address these issues through the design of new materials. Synthetic chemistry offers powerful tools for manipulating the magnificent flexibility of the perovskite lattice to expand the number of functional analogues to APbI3. To highlight improvements that should be targeted in new materials, here we discuss the intrinsic instability and toxicity of 3D lead-halide perovskites. We consider possible sources of these instabilities and propose methods to overcome them through synthetic design. We also discuss new materials developed for realizing the exceptional photophysical properties of lead-halide perovskites in more environmentally benign materials. In this Forum Article, we provide a brief overview of the field with a focus on our group's contributions to identifying and addressing problems inherent to 3D lead-halide perovskites.

A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications.

Despite the remarkable rise in efficiencies of solar cells containing the lead-halide perovskite absorbers RPbX3 (R = organic cation; X = Br(-) or I(-)), the toxicity of lead remains a concern for the large-scale implementation of this technology. This has spurred the search for lead-free materials with similar optoelectronic properties. Here, we use the double-perovskite structure to incorporate nontoxic Bi(3+) into the perovskite lattice in Cs2AgBiBr6 (1). The solid shows a long room-temperature fundamental photoluminescence (PL) lifetime of ca. 660 ns, which is very encouraging for photovoltaic applications. Comparison between single-crystal and powder PL decay curves of 1 suggests inherently high defect tolerance. The material has an indirect bandgap of 1.95 eV, suited for a tandem solar cell. Furthermore, 1 is significantly more heat and moisture stable compared to (MA)PbI3. The extremely promising optical and physical properties of 1 shown here motivate further exploration of both inorganic and hybrid halide double perovskites for photovoltaics and other optoelectronics.