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.

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.

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.

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.

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.

Electronic structure of dipeptides in the gas-phase and as an adsorbed monolayer.

Peptide-based molecular electronic devices are promising due to the large diversity and unique electronic properties of biomolecules. These electronic properties can change considerably with peptide structure, allowing diverse design possibilities. In this work, we explore the effect of the side-chain of the peptide on its electronic properties, by using both experimental and computational tools to detect the electronic energy levels of two model peptides. The peptides include 2Ala and 2Trp as well as their 3-mercaptopropionic acid linker which is used to form monolayers on an Au surface. Specifically, we compare experimental ultraviolet photoemission spectroscopy measurements with density functional theory based computational results. By analyzing differences in frontier energy levels and molecular orbitals between peptides in gas-phase and in a monolayer on gold, we find that the electronic properties of the peptide side-chain are maintained during binding of the peptide to the gold substrate. This indicates that the energy barrier for the peptide electron transport can be tuned by the amino acid compositions, which suggests a route for structural design of peptide-based electronic devices.

Hybrid Organic-Inorganic Perovskites on the Move.

Hybrid organic-inorganic perovskites (HOIPs) are crystals with the structural formula ABX3, where A, B, and X are organic and inorganic ions, respectively. While known for several decades, HOIPs have only in recent years emerged as extremely promising semiconducting materials for solar energy applications. In particular, power-conversion efficiencies of HOIP-based solar cells have improved at a record speed and, after only little more than 6 years of photovoltaics research, surpassed the 20% threshold, which is an outstanding result for a solution-processable material. It is thus of fundamental importance to reveal physical and chemical phenomena that contribute to, or limit, these impressive photovoltaic efficiencies. To understand charge-transport and light-absorption properties of semiconducting materials, one often invokes a lattice of ions displaced from their static positions only by harmonic vibrations. However, a preponderance of recent studies suggests that this picture is not sufficient for HOIPs, where a variety of structurally dynamic effects, beyond small harmonic vibrations, arises already at room temperature. In this Account, we focus on these effects. First, we review structure and bonding in HOIPs and relate them to the promising charge-transport and absorption properties of these materials, in terms of favorable electronic properties. We point out that HOIPs are much "softer" mechanically, compared to other efficient solar-cell materials, and that this can result in large ionic displacements at room temperature. We therefore focus next on dynamic structural effects in HOIPs, going beyond a static band-structure picture. Specifically, we discuss pertinent experimental and theoretical findings as to phase-transition behavior and molecular/octahedral rearrangements. We then discuss atomic diffusion phenomena in HOIPs, with an emphasis on the migration of intrinsic and extrinsic ionic species. From this combined perspective, HOIPs appear as highly dynamic materials, in which structural fluctuations and long-range ionic motion have an unusually strong impact on charge-transport and optical properties. We highlight the potential implications of these effects for several intriguing phenomenological observations, ranging from scattering mechanisms and lifetimes of charge carriers to light-induced structural effects and ionic conduction.

Local Polar Fluctuations in Lead Halide Perovskite Crystals.

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH_{3}NH_{3}PbBr_{3}) and all-inorganic (CsPbBr_{3}) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr_{3}.

High Chloride Doping Levels Stabilize the Perovskite Phase of Cesium Lead Iodide.

Cesium lead iodide possesses an excellent combination of band gap and absorption coefficient for photovoltaic applications in its perovskite phase. However, this is not its equilibrium structure under ambient conditions. In air, at ambient temperature it rapidly transforms to a nonfunctional, so-called yellow phase. Here we show that chloride doping, particularly at levels near the solubility limit for chloride in a cesium lead iodide host, provides a new approach to stabilizing the functional perovskite phase. In order to achieve high doping levels, we first co-deposit colloidal nanocrystals of pure cesium lead chloride and cesium lead iodide, thereby ensuring nanometer-scale mixing even at compositions that potentially exceed the bulk miscibility of the two phases. The resulting nanocrystal solid is subsequently fused into a polycrystalline thin film by chemically induced, room-temperature sintering. Spectroscopy and X-ray diffraction indicate that the chloride is further dispersed during sintering and a polycrystalline mixed phase is formed. Using density functional theory (DFT) methods in conjunction with nudged elastic band techniques, low-energy pathways for interstitial chlorine diffusion into a majority-iodide lattice were identified, consistent with the facile diffusion and fast halide exchange reactions observed. By comparison to DFT-calculated values (with the PBE exchange-correlation functional), the relative change in band gap and the lattice contraction are shown to be consistent with a Cl/I ratio of a few percent in the mixed phase. At these incorporation levels, the half-life of the functional perovskite phase in a humid atmosphere increases by more than an order of magnitude.

Reliable energy level alignment at physisorbed molecule-metal interfaces from density functional theory.

A key quantity for molecule-metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal-molecule interfaces. The method builds on the "DFT+Σ" approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule-metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.

Theory of hydrogen migration in organic-inorganic halide perovskites.

Solar cells based on organic-inorganic halide perovskites have recently been proven to be remarkably efficient. However, they exhibit hysteresis in their current-voltage curves, and their stability in the presence of water is problematic. Both issues are possibly related to a diffusion of defects in the perovskite material. By using first-principles calculations based on density functional theory, we study the properties of an important defect in hybrid perovskites-interstitial hydrogen. We show that differently charged defects occupy different crystal sites, which may allow for ionization-enhanced defect migration following the Bourgoin-Corbett mechanism. Our analysis highlights the structural flexibility of organic-inorganic perovskites: successive iodide displacements, combined with hydrogen bonding, enable proton diffusion with low migration barriers. These findings indicate that hydrogen defects can be mobile and thus highly relevant for the performance of perovskite solar cells.

Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.

Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

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.

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.

Dimensionality effects in the electronic structure of organic semiconductors consisting of polar repeat units.

In conjugated organic molecules, excitation gaps typically decrease reciprocally with increasing the number of repeat units, n. This usually holds for individual molecules as well as for the corresponding bulk materials. Here, we show using density-functional theory calculations that a qualitatively different evolution is found for layers built from molecules consisting of polar repeat units. Whereas a 1/n-dependence is still observed in the case of isolated polar molecules, the global gap decreases essentially linearly with n in the corresponding 2D-periodic systems and vanishes beyond a certain molecular length, with the frontier states being localized at opposite ends of the layer. The latter is accompanied by a saturation of the dipole moment per molecule, an effect not observed in the isolated polar molecules. Interestingly, in both cases the limit of the gap for long (but finite) molecules differs qualitatively from that of infinite length obtained in 1D-periodic and 3D-periodic calculations, the latter serving as models for polymers and the bulk. We rationalize these dimensionality effects as a consequence of the potential gradient within the finite-length layers. They arise from the collective action of intra-molecular dipoles in the 2D periodic layers and can be traced back to surface effects.

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.

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.