Douglas H. Fabini

Electronic structure and photovoltaic application of BiI3

Rapid recent improvement in photovoltaic efficiency in hybrid lead halide perovskite materials has provided the impetus for understanding other, related main-group halide systems. Here, we show that the closely related but less toxic bismuth iodide BiI3 can show promising optoelectronic properties. Layered binary BiI3 is used here as the active layer in planar solar cell architectures (efficiency approximately 0.3%). Experimental and computational studies of absolute band positions of BiI3 are also presented, to help in the rational design of device architectures that would allow efficient charge transfer at the interfaces.

Temperature-Dependent Polarization in Field-Effect Transport and Photovoltaic Measurements of Methylammonium Lead Iodide

While recent improvements in the reported peak power conversion efficiency (PCE) of hybrid organic-inorganic perovskite solar cells have been truly astonishing, there are many fundamental questions about the electronic behavior of these materials. Here we have studied a set of electronic devices employing methylammonium lead iodide ((MA)PbI3) as the active material and conducted a series of temperature-dependent measurements. Field-effect transistor, capacitor, and photovoltaic cell measurements all reveal behavior consistent with substantial and strongly temperature-dependent polarization susceptibility in (MA)PbI3 at temporal and spatial scales that significantly impact functional behavior. The relative PCE of (MA)PbI3 photovoltaic cells is observed to reduce drastically with decreasing temperature, suggesting that such polarization effects could be a prerequisite for high-performance device operation.

Making sanitation count: developing and testing a device for assessing latrine use in low-income settings

While efforts are underway to expand latrine coverage to an estimated 2.6 billion people who lack access to improved sanitation, there is evidence that actual use of latrines is suboptimal, limiting the potential health and environmental gains from containment of human excreta. We developed a passive latrine use monitor (PLUM) and compared its ability to measure latrine activity with structured observation. Each PLUM consisted of a passive infrared motion detector, microcontroller, data storage card, and batteries mounted in a small plastic housing that was positioned inside the latrine. During a field trial in Orissa, India, with ∼115 households, the number of latrine events measured by the PLUMs was in good agreement with that measured by trained observers during 5 h of structured observation per device per week. A significant finding was that the presence of a human observer was associated with a statistically significant increase in the number of latrine events, i.e., the users modified their behavior in response to the observer. Another advantage of the PLUM was the ability to measure activity continuously for an entire week. A shortcoming of the PLUM was the inability to separate latrine events that occurred in immediate succession, leading to possible undercounting during high-traffic periods. The PLUM is a promising technology that can provide detailed measures of latrine use to improve the understanding of sanitation behaviors and how to modify them and for assessing the intended health, livelihood, and environmental benefits of improved sanitation.

Dielectric and Thermodynamic Signatures of Low-Temperature Glassy Dynamics in the Hybrid Perovskites CH3NH3PbI3 and HC(NH2)2PbI3

Hybrid main group halide perovskites hold great technological promise in optoelectronic applications and present rich and complex evolution of structure and dynamics. Here we present low-temperature dielectric measurements and calorimetry of APbI3 [A = CH3NH3(+), HC(NH2)2(+)] that suggest glassy behavior on cooling. In both compounds, the dielectric loss displays frequency-dependent peaks below 100 K characteristic of a glassy slowing of relaxation dynamics, with HC(NH2)2PbI3 exhibiting greater glass fragility. Consistent with quenched disorder, the low-temperature heat capacity of both perovskites deviates substantially from the ∼T(3) acoustic phonon contribution predicted by the Debye model. We suggest that static disorder of the A-site molecular cation, potentially coupled to local distortions of the Pb-I sublattice, is responsible for these phenomena. The distinct low-temperature dynamics observed in these two perovskites suggest qualitative differences in the interaction between the molecular cation and the surrounding inorganic framework, with potential implications for defect screening and device performance at ambient temperatures.

Dynamic Stereochemical Activity of the Sn2+ Lone Pair in Perovskite CsSnBr3

Stable s(2) lone pair electrons on heavy main-group elements in their lower oxidation states drive a range of important phenomena, such as the emergence of polar ground states in some ferroic materials. Here we study the perovskite halide CsSnBr3 as an embodiment of the broader materials class. We show that lone pair stereochemical activity due to the Sn(2+) s(2) lone pair causes a crystallographically hidden, locally distorted state to appear upon warming, a phenomenon previously referred to as emphanisis. The synchrotron X-ray pair distribution function acquired between 300 and 420 K reveals emerging asymmetry in the nearest-neighbor Sn-Br correlations, consistent with dynamic Sn(2+) off-centering, despite there being no evidence of any deviation from the average cubic structure. Computation based on density functional theory supports the finding of a lattice instability associated with dynamic off-centering of Sn(2+) in its coordination environment. Photoluminescence measurements reveal an unusual blue-shift with increasing temperature, closely linked to the structural evolution. At low temperatures, the structures reflect the influence of octahedral rotation. A continuous transition from an orthorhombic structure (Pnma, no. 62) to a tetragonal structure (P4/mbm, no. 127) is found around 250 K, with a final, first-order transformation at 286 K to the cubic structure (Pm3̅m, no. 221).

Main-Group Halide Semiconductors Derived from Perovskite: Distinguishing Chemical, Structural, and Electronic Aspects

Main-group halide perovskites have generated much excitement of late because of their remarkable optoelectronic properties, ease of preparation, and abundant constituent elements, but these curious and promising materials differ in important respects from traditional semiconductors. The distinguishing chemical, structural, and electronic features of these materials present the key to understanding the origins of the optoelectronic performance of the well-studied hybrid organic-inorganic lead halides and provide a starting point for the design and preparation of new functional materials. Here we review and discuss these distinguishing features, among them a defect-tolerant electronic structure, proximal lattice instabilities, labile defect migration, and, in the case of hybrid perovskites, disordered molecular cations. Additionally, we discuss the preparation and characterization of some alternatives to the lead halide perovskites, including lead-free bismuth halides and hybrid materials with optically and electronically active organic constituents.

Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide

The structure of the hybrid perovskite HC(NH2 )2 PbI3 (formamidinium lead iodide) reflects competing interactions associated with molecular motion, hydrogen bonding tendencies, thermally activated soft octahedral rotations, and the propensity for the Pb2+ lone pair to express its stereochemistry. High-resolution synchrotron X-ray powder diffraction reveals a continuous transition from the cubic α-phase (Pm3‾ m, #221) to a tetragonal β-phase (P4/mbm, #127) at around 285 K, followed by a first-order transition to a tetragonal γ-phase (retaining P4/mbm, #127) at 140 K. An unusual reentrant pseudosymmetry in the β-to-γ phase transition is seen that is also reflected in the photoluminescence. Around room temperature, the coefficient of volumetric thermal expansion is among the largest for any extended crystalline solid.

Universal Dynamics of Molecular Reorientation in Hybrid Lead Iodide Perovskites

The role of organic molecular cations in the high-performance perovskite photovoltaic absorbers, methylammonium lead iodide (MAPbI3) and formamidinium lead iodide (FAPbI3), has been an enigmatic subject of great interest. Beyond aiding in the ease of processing of thin films for photovoltaic devices, there have been suggestions that many of the remarkable properties of the halide perovskites can be attributed to the dipolar nature and the dynamic behavior of these cations. Here, we establish the dynamics of the molecular cations in FAPbI3 between 4 K and 340 K and the nature of their interaction with the surrounding inorganic cage using a combination of solid state nuclear magnetic resonance and dielectric spectroscopies, neutron scattering, calorimetry, and ab initio calculations. Detailed comparisons with the reported temperature dependence of the dynamics of MAPbI3 are then carried out which reveal the molecular ions in the two different compounds to exhibit very similar rotation rates (≈8 ps) at room temperature, despite differences in other temperature regimes. For FA, rotation about the N···N axis, which reorients the molecular dipole, is the dominant motion in all phases, with an activation barrier of ≈21 meV in the ambient phase, compared to ≈110 meV for the analogous dipole reorientation of MA. Geometrical frustration of the molecule-cage interaction in FAPbI3 produces a disordered γ-phase and subsequent glassy freezing at yet lower temperatures. Hydrogen bonds suggested by atom-atom distances from neutron total scattering experiments imply a substantial role for the molecules in directing structure and dictating properties. The temperature dependence of reorientation of the dipolar molecular cations systematically described here can clarify various hypotheses including those of large-polaron charge transport and fugitive electron spin polarization that have been invoked in the context of these unusual materials.

Mapping Induced Residential Demand for Electricity in Kenya

Despite substantial gains in the past few decades, 550 million people in sub-Saharan Africa still lack access to electricity. Rural areas present the largest electrification challenge, with access levels below 12% in most countries. Public rural electrification efforts, where undertaken, have generally effected slow and limited change. Further, to motivate the substantial investment required for traditional large-scale generation and transmission projects, strong demand for electricity services is required, and this demand is not easily demonstrated in rural African settings in which little data and substantial uncertainty exist. In this paper, we develop a predictive model for mapping induced residential demand for electricity -- the hypothetical demand that would exist if access to electricity services were made available. We apply this model on a fine geographic basis to Kenya to demonstrate the applicability of the approach to informing public or private electrification efforts. Together with spatially explicit cost models for generation, transmission, and distribution, these induced demand predictions can be used to evaluate various technology options, business models, and tariff structures, or to guide public sector electrification program development.

Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide

The temperature-dependent structure evolution of the hybrid halide perovskite compounds, formamidinium tin iodide (FASnI3, FA+ = CH[NH2]2+) and formamidinium lead bromide (FAPbBr3), has been monitored using high-resolution synchrotron X-ray powder diffraction between 300 and 100 K. The data are consistent with a transition from cubic Pm3m (No. 221) to tetragonal P4/mbm (No. 127) for both materials upon cooling; this occurs for FAPbBr3 between 275 and 250 K, and for FASnI3 between 250 and 225 K. Upon further cooling, between 150 and 125 K, both materials undergo a transition to an orthorhombic Pnma (No. 62) structure. The transitions are confirmed by calorimetry and dielectric measurements. In the tetragonal regime, the coefficients of volumetric thermal expansion of FASnI3 and FAPbBr3 are among the highest recorded for any extended inorganic crystalline solid, reaching 219 ppm K-1 for FASnI3 at 225 K. Atomic displacement parameters of all atoms for both materials suggest dynamic motion is occurring in the inorganic sublattice due to the flexibility of the inorganic network and dynamic lone pair stereochemical activity on the B-site. Unusual pseudocubic behavior is displayed in the tetragonal phase of the FAPbBr3, similar to that previously observed in FAPbI3.