Disentangling the effects of structure and lone-pair electrons in the lattice dynamics of halide perovskites.

Halide perovskites show great optoelectronic performance, but their favorable properties are paired with unusually strong anharmonicity. It was proposed that this combination derives from the ns2 electron configuration of octahedral cations and associated pseudo-Jahn-Teller effect. We show that such cations are not a prerequisite for the strong anharmonicity and low-energy lattice dynamics encountered in these materials. We combine X-ray diffraction, infrared and Raman spectroscopies, and molecular dynamics to contrast the lattice dynamics of CsSrBr3 with those of CsPbBr3, two compounds that are structurally similar but with the former lacking ns2 cations with the propensity to form electron lone pairs. We exploit low-frequency diffusive Raman scattering, nominally symmetry-forbidden in the cubic phase, as a fingerprint of anharmonicity and reveal that low-frequency tilting occurs irrespective of octahedral cation electron configuration. This highlights the role of structure in perovskite lattice dynamics, providing design rules for the emerging class of soft perovskite semiconductors.

Temperature-transferable tight-binding model using a hybrid-orbital basis.

Finite-temperature calculations are relevant for rationalizing material properties, yet they are computationally expensive because large system sizes or long simulation times are typically required. Circumventing the need for performing many explicit first-principles calculations, tight-binding and machine-learning models for the electronic structure emerged as promising alternatives, but transferability of such methods to elevated temperatures in a data-efficient way remains a great challenge. In this work, we suggest a tight-binding model for efficient and accurate calculations of temperature-dependent properties of semiconductors. Our approach utilizes physics-informed modeling of the electronic structure in the form of hybrid-orbital basis functions and numerically integrating atomic orbitals for the distance dependence of matrix elements. We show that these design choices lead to a tight-binding model with a minimal amount of parameters that are straightforwardly optimized using density functional theory or alternative electronic-structure methods. The temperature transferability of our model is tested by applying it to existing molecular-dynamics trajectories without explicitly fitting temperature-dependent data and comparison with density functional theory. We utilize it together with machine-learning molecular dynamics and hybrid density functional theory for the prototypical semiconductor gallium arsenide. We find that including the effects of thermal expansion on the onsite terms of the tight-binding model is important in order to accurately describe electronic properties at elevated temperatures in comparison with experiment.

Alloying Effects on Charge-Carrier Transport in Silver-Bismuth Double Perovskites.

Alloying is widely adopted for tuning the properties of emergent semiconductors for optoelectronic and photovoltaic applications. So far, alloying strategies have primarily focused on engineering bandgaps rather than optimizing charge-carrier transport. Here, we demonstrate that alloying may severely limit charge-carrier transport in the presence of localized charge carriers (e.g., small polarons). By combining reflection-transmission and optical pump-terahertz probe spectroscopy with first-principles calculations, we investigate the interplay between alloying and charge-carrier localization in Cs2AgSbxBi1-xBr6 double perovskite thin films. We show that the charge-carrier transport regime strongly determines the impact of alloying on the transport properties. While initially delocalized charge carriers probe electronic bands formed upon alloying, subsequently self-localized charge carriers probe the energetic landscape more locally, thus turning an alloy's low-energy sites (e.g., Sb sites) into traps, which dramatically deteriorates transport properties. These findings highlight the inherent limitations of alloying strategies and provide design tools for newly emerging and highly efficient semiconductors.

Static and Dynamic Disorder in Formamidinium Lead Bromide Single Crystals.

We show that formamidinium-based crystals are distinct from methylammonium-based halide perovskite crystals because their inorganic sublattice exhibits intrinsic local static disorder that coexists with a well-defined average crystal structure. Our study combines terahertz-range Raman scattering with single-crystal X-ray diffraction and first-principles calculations to probe the evolution of inorganic sublattice dynamics with temperature in the range of 10-300 K. The temperature evolution of the Raman spectra shows that low-temperature, local static disorder strongly affects the crystal structural dynamics and phase transitions at higher temperatures.

Accurate non-adiabatic couplings from optimally tuned range-separated hybrid functionals.

Precise theoretical calculations of non-adiabatic couplings, which describe the interaction between two Born-Oppenheimer surfaces, are important for the modeling of radiationless decay mechanisms in photochemical processes. Here, we demonstrate that accurate non-adiabatic couplings can be calculated in the framework of linear-response time-dependent density functional theory by using non-empirical, optimally tuned range-separated hybrid (OT-RSH) functionals. We focus on molecular radicals, in which ultrafast non-radiative decay plays a crucial role, to find that the OT-RSH functional compares well to wave-function-based reference data and competes with the accuracy of semi-empirical CAM-B3LYP calculations. Our findings show that the OT-RSH approach yields very accurate non-adiabatic couplings and, therefore, provides a computationally efficient alternative to wave-function-based techniques.

Optically Induced Long-Lived Chirality Memory in the Color-Tunable Chiral Lead-Free Semiconductor (R)/(S)-CHEA4Bi2BrxI10-x (x = 0-10).

Hybrid organic-inorganic networks that incorporate chiral molecules have attracted great attention due to their potential in semiconductor lighting applications and optical communication. Here, we introduce a chiral organic molecule (R)/(S)-1-cyclohexylethylamine (CHEA) into bismuth-based lead-free structures with an edge-sharing octahedral motif, to synthesize chiral lead-free (R)/(S)-CHEA4Bi2BrxI10-x crystals and thin films. Using single-crystal X-ray diffraction measurements and density functional theory calculations, we identify crystal and electronic band structures. We investigate the materials' optical properties and find circular dichroism, which we tune by the bromide-iodide ratio over a wide wavelength range, from 300 to 500 nm. We further employ transient absorption spectroscopy and time-correlated single photon counting to investigate charge carrier dynamics, which show long-lived excitations with optically induced chirality memory up to tens of nanosecond timescales. Our demonstration of chirality memory in a color-tunable chiral lead-free semiconductor opens a new avenue for the discovery of high-performance, lead-free spintronic materials with chiroptical functionalities.

Anharmonic Lattice Dynamics in Sodium Ion Conductors.

We employ terahertz-range temperature-dependent Raman spectroscopy and first-principles lattice dynamical calculations to show that the undoped sodium ion conductors Na3PS4 and isostructural Na3PSe4 both exhibit anharmonic lattice dynamics. The anharmonic effects in the compounds involve coupled host lattice-Na+ ion dynamics that drive the tetragonal-to-cubic phase transition in both cases, but with a qualitative difference in the anharmonic character of the transition. Na3PSe4 shows an almost purely displacive character with the soft modes disappearing in the cubic phase as the change in symmetry shifts these modes to the Raman-inactive Brillouin zone boundary. Na3PS4 instead shows an order-disorder character in the cubic phase, with the soft modes persisting through the phase transition and remaining Raman active in the cubic phase, violating Raman selection rules for that phase. Our findings highlight the important role of coupled host lattice-mobile ion dynamics in vibrational instabilities that are coincident with the exceptional conductivity of these Na+ ion conductors.

Probing the Disorder Inside the Cubic Unit Cell of Halide Perovskites from First-Principles.

Strong deviations in the finite temperature atomic structure of halide perovskites from their average geometry can have profound impacts on optoelectronic and other device-relevant properties. Detailed mechanistic understandings of these structural fluctuations and their consequences remain, however, limited by the experimental and theoretical challenges involved in characterizing strongly anharmonic vibrational characteristics and their impact on other properties. We overcome some of these challenges by a theoretical characterization of the vibrational interactions that occur among the atoms in the prototypical cubic CsPbBr3. Our investigation based on first-principles molecular dynamics calculations finds that the motions of neighboring Cs-Br atoms interlock, which appears as the most likely Cs-Br distance being significantly shorter than what is inferred from an ideal cubic structure. This form of dynamic Cs-Br coupling coincides with very shallow dynamic potential wells for Br motions that occur across a locally and dynamically disordered energy landscape. We reveal an interesting dynamic coupling mechanism among the atoms within the nominal unit cell of cubic CsPbBr3 and quantify the important local structural fluctuations on an atomic scale.

Transversal Halide Motion Intensifies Band-To-Band Transitions in Halide Perovskites.

Despite their puzzling vibrational characteristics that include strong signatures of anharmonicity and thermal disorder already around room temperature, halide perovskites (HaPs) exhibit favorable optoelectronic properties for applications in photovoltaics and beyond. Whether these vibrational properties are advantageous or detrimental to their optoelectronic properties remains, however, an important open question. Here, this issue is addressed by investigation of the finite-temperature optoelectronic properties in the prototypical cubic CsPbBr3 , using first-principles molecular dynamics based on density-functional theory. It is shown that the dynamic flexibility associated with HaPs enables the so-called transversality, which manifests as a preference for large halide displacements perpendicular to the Pb-Br-Pb bonding axis. The authors find that transversality is concurrent with vibrational anharmonicity and leads to a rapid rise in the joint density of states, which is favorable for photovoltaics since this implies sharp optical absorption profiles. These findings are contrasted to the case of PbTe, a material that shares several key properties with CsPbBr3 but cannot exhibit any transversality and, hence, is found to exhibit much wider band-edge distributions. The authors conclude that the dynamic structural flexibility in HaPs and their unusual vibrational characteristics might not just be a mere coincidence, but play active roles in establishing their favorable optoelectronic properties.

A single atom change turns insulating saturated wires into molecular conductors.

We present an efficient strategy to modulate tunnelling in molecular junctions by changing the tunnelling decay coefficient, ß, by terminal-atom substitution which avoids altering the molecular backbone. By varying X = H, F, Cl, Br, I in junctions with S(CH2)(10-18)X, current densities (J) increase >4 orders of magnitude, creating molecular conductors via reduction of ß from 0.75 to 0.25 Å-1. Impedance measurements show tripled dielectric constants (εr) with X = I, reduced HOMO-LUMO gaps and tunnelling-barrier heights, and 5-times reduced contact resistance. These effects alone cannot explain the large change in ß. Density-functional theory shows highly localized, X-dependent potential drops at the S(CH2)nX//electrode interface that modifies the tunnelling barrier shape. Commonly-used tunnelling models neglect localized potential drops and changes in εr. Here, we demonstrate experimentally that [Formula: see text], suggesting highly-polarizable terminal-atoms act as charge traps and highlighting the need for new charge transport models that account for dielectric effects in molecular tunnelling junctions.

Accurate Molecular Geometries in Complex Excited-State Potential Energy Surfaces from Time-Dependent Density Functional Theory.

The interplay of electronic excitations and structural changes in molecules impacts nonradiative decay and charge transfer in the excited state, thus influencing excited-state lifetimes and photocatalytic reaction rates in optoelectronic and energy devices. To capture such effects requires computational methods providing an accurate description of excited-state potential energy surfaces and geometries. We suggest time-dependent density functional theory using optimally tuned range-separated hybrid (OT-RSH) functionals as an accurate approach to obtain excited-state molecular geometries. We show that OT-RSH provides accurate molecular geometries in excited-state potential energy surfaces that are complex and involve an interplay of local and charge-transfer excitations, for which conventional semilocal and hybrid functionals fail. At the same time, the nonempirical OT-RSH approach maintains the high accuracy of parametrized functionals (e.g., B3LYP) for predicting excited-state geometries of small organic molecules showing valence excited states.

Fast and Anomalous Exciton Diffusion in Two-Dimensional Hybrid Perovskites.

Two-dimensional hybrid perovskites are currently in the spotlight of condensed matter and nanotechnology research due to their intriguing optoelectronic and vibrational properties with emerging potential for light-harvesting and light-emitting applications. While it is known that these natural quantum wells host tightly bound excitons, the mobilities of these fundamental optical excitations at the heart of the optoelectronic applications are barely explored. Here, we directly monitor the diffusion of excitons through ultrafast emission microscopy from liquid helium to room temperature in hBN-encapsulated two-dimensional hybrid perovskites. We find very fast diffusion with characteristic hallmarks of free exciton propagation for all temperatures above 50 K. In the cryogenic regime, we observe nonlinear, anomalous behavior with an exceptionally rapid expansion of the exciton cloud followed by a very slow and even negative effective diffusion. We discuss our findings in view of efficient exciton-phonon coupling, highlighting two-dimensional hybrids as promising platforms for basic research and optoelectronic applications.

Anharmonic Lattice Vibrations in Small-Molecule Organic Semiconductors.

The intermolecular lattice vibrations in small-molecule organic semiconductors have a strong impact on their functional properties. Existing models treat the lattice vibrations within the harmonic approximation. In this work, polarization-orientation (PO) Raman measurements are used to monitor the temperature-evolution of the symmetry of lattice vibrations in anthracene and pentacene single crystals. Combined with first-principles calculations, it is shown that at 10 K, the lattice dynamics of the crystals are indeed harmonic. However, as the temperature is increased, specific lattice modes gradually lose their PO dependence and become more liquid-like. This finding is indicative of a dynamic symmetry breaking of the crystal structure and shows clear evidence of the strongly anharmonic nature of these vibrations. Pentacene also shows an apparent phase transition between 80 and 150 K, indicated by a change in the vibrational symmetry of one of the lattice modes. These findings lay the groundwork for accurate predictions of the electronic properties of high-mobility organic semiconductors at room temperature.

Dynamic shortening of disorder potentials in anharmonic halide perovskites.

Halide perovskites are semiconductors that exhibit sharp optical absorption edges and small Urbach energies allowing for efficient collection of sunlight in thin-film photovoltaic devices. However, halide perovskites also exhibit large nuclear anharmonic effects and disorder, which is unusual for efficient optoelectronic materials and difficult to rationalize in view of the small Urbach energies that indicate a low amount of disorder. To address this important issue, the disorder potential induced for electronic states by the nuclear dynamics in various paradigmatic halide perovskites is studied with molecular dynamics and density functional theory. We find that the disorder potential is dynamically shortened due to the nuclear motions in the perovskite, such that it is short-range correlated, which is shown to lead to favorable distributions of band edge energies. This dynamic mechanism allows for sharp optical absorption edges and small Urbach energies, which are highly desired properties of any solar absorber material.

Interplay of Collective Electrostatic Effects and Level Alignment Dictates the Tunneling Rates across Halogenated Aromatic Monolayer Junctions.

Predictions about the electrical conductance across molecular junctions based on self-assembled monolayers (SAMs) are often made from the SAM precursor properties. Collective electrostatic effects, however, in a densely packed SAM can override these predictions. We studied, experimentally and theoretically, molecular tunneling junctions based on thiolate SAMs with an aromatic biphenyl backbone and variable, highly polarizable halogen termini X (S-(C6H5)2X; X = H, F, Cl, Br, or I). We found that the halogen-terminated systems show tunneling rates and dielectric behavior that are independent of X despite the large change in the electronegativity of the terminal atom. Using density functional theory, we show that collective electrostatic effects result in modulations of the electrostatic potential that are strongly confined spatially along the direction of charge transport, thereby rendering the role of the halogen atoms insignificant for SAMs with conjugated backbones.

Breakdown of the Static Picture of Defect Energetics in Halide Perovskites: The Case of the Br Vacancy in CsPbBr3.

We consider the Br vacancy in CsPbBr3 as a prototype for the impact of structural dynamics on defect energetics in halide perovskites (HaPs). Using first-principles molecular dynamics based on density functional theory, we find that the static picture of defect energetics breaks down; the energy level associated with a Br vacancy is found to be intrinsically dynamic, oscillating by as much as 1 eV on the picosecond time scale at room temperature. These significant energy fluctuations are correlated with the distance between the neighboring Pb atoms across the vacancy and with the electrostatic potential at these Pb atomic sites. We expect this unusually strong coupling of structural dynamics and defect energetics to bear important implications for both experimental and theoretical analyses of defect characteristics in HaPs. It may also hold significant ramifications for carrier transport and defect tolerance in this class of photovoltaic materials.

Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements.

Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.

How Lattice and Charge Fluctuations Control Carrier Dynamics in Halide Perovskites.

Here we develop a microscopic approach aimed at the description of a suite of physical effects related to carrier transport in, and the optical properties of, halide perovskites. Our theory is based on the description of the nuclear dynamics to all orders and goes beyond the common assumption of linear electron-phonon coupling in describing the carrier dynamics and band gap characteristics. When combined with first-principles calculations and applied to the prototypical MAPbI3 system, our theory explains seemingly disparate experimental findings associated with both the charge-carrier mobility and optical absorption properties, including their temperature dependencies. Our findings demonstrate that orbital-overlap fluctuations in the lead-halide structure plays a significant role in determining the optoelectronic features of halide perovskites.

Intermediate Bands in Zero-Dimensional Antimony Halide Perovskites.

Using density functional theory, the structural and electronic-structure properties of a recently discovered, zero-dimensional antimony halide perovskite are studied. It is found that the herein considered material EtPySbBr6 exhibits very promising electronic-structure properties: a direct band gap close to the peak of the solar spectrum and effective masses allowing for efficient carrier transport of electrons in particular. These results are rationalized by analysis of the electronic structure, which reveals the formation of intermediate bands due to orbital-hybridization effects of the Sb s-states. This study shows that the formation of intermediate bands can lead to highly favorable electronic-structure properties of zero-dimensional perovskites and discusses the possibility of fabricating lead-free halide perovskites with promising optoelectronic properties by targeted substitution of ions and emergence of intermediate bands. These insights are important when understanding and further enhancing the capabilities of antimony and other promising lead-free compounds.