Nuclear Quadrupolar Resonance Structural Characterization of Halide Perovskites and Perovskitoids: A Roadmap from Electronic Structure Calculations for Lead-Iodide-Based Compounds.

Metal halide perovskites, including some of their related perovskitoid structures, form a semiconductor class of their own, which is arousing ever-growing interest from the scientific community. With halides being involved in the various structural arrangements, namely, pure corner-sharing MX (M is metal and X is halide) octahedra, for perovskite networks, or alternatively a combination of corner-, edge-, and/or face-sharing for related perovskitoids, they represent the ideal probe for characterizing the way octahedra are linked together. Well known for their inherently large quadrupolar constants, which is detrimental to the resolution of nuclear magnetic resonance spectroscopy, most abundant halide isotopes (Cl, Br, I) are in turn attractive for magnetic field-free nuclear quadrupolar resonance (NQR) spectroscopy.

Enhancing Interlayer Charge Transport of Two-Dimensional Perovskites by Structural Stabilization via Fluorine Substitution.

Two-dimensional lead-halide perovskites provide a more robust alternative to three-dimensional perovskites in solar energy and optoelectronic applications due to increased chemical stability afforded by interlayer ligands. At the same time, the ligands create barriers for interlayer charge transport, reducing device performance. Using a recently developed ab initio simulation methodology, we demonstrate that ligand fluorination can enhance both hole and electron mobility by 1-2 orders of magnitude.

Non-equilibrium transport in polymer mixed ionic-electronic conductors at ultrahigh charge densities.

Conducting polymers are mixed ionic-electronic conductors that are emerging candidates for neuromorphic computing, bioelectronics and thermoelectrics. However, fundamental aspects of their many-body correlated electron-ion transport physics remain poorly understood. Here we show that in p-type organic electrochemical transistors it is possible to remove all of the electrons from the valence band and even access deeper bands without degradation.

Elucidating the Non-Covalent Interactions that Trigger Interdigitation in Lead-Halide Layered Hybrid Perovskites.

Two-dimensional (2D) hybrid organic-inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces.

Interlayer Charge Transport in 2D Lead Halide Perovskites from First Principles.

We report on the implementation of a versatile projection-operator diabatization approach to calculate electronic coupling integrals in layered periodic systems. The approach is applied to model charge transport across the saturated organic spacers in two-dimensional (2D) lead halide perovskites. The calculations yield out-of-plane charge transfer rates that decay exponentially with the increasing length of the alkyl chain, range from a few nanoseconds to milliseconds, and are supportive of a hopping mechanism.

Persistent Ion Accumulation at Interfaces Improves the Performance of Perovskite Solar Cells.

The mixed ionic-electronic nature of lead halide perovskites makes their performance in solar cells complex in nature. Ion migration is often associated with negative impacts-such as hysteresis or device degradation-leading to significant efforts to suppress ionic movement in perovskite solar cells. In this work, we demonstrate that ion trapping at the perovskite/electron transport layer interface induces band bending, thus increasing the built-in potential and open-circuit voltage of the device.

Revealing Weak Dimensional Confinement Effects in Excitonic Silver/Bismuth Double Perovskites.

Lead-free perovskites are attracting increasing interest as nontoxic materials for advanced optoelectronic applications. Here, we report on a family of silver/bismuth bromide double perovskites with lower dimensionality obtained by incorporating phenethylammonium (PEA) as an organic spacer, leading to the realization of two-dimensional double perovskites in the form of (PEA)AgBiBr ( = 1) and the first reported (PEA)CsAgBiBr ( = 2). In contrast to the situation prevailing in lead halide perovskites, we find a rather weak influence of electronic and dielectric confinement on the photophysics of the lead-free double perovskites, with both the 3D CsAgBiBr and the 2D = 1 and = 2 materials being dominated by strong excitonic effects.

Tetrazine molecules as an efficient electronic diversion channel in 2D organic-inorganic perovskites.

Taking advantage of an innovative design concept for layered halide perovskites with active chromophores acting as organic spacers, we present here the synthesis of two novel two-dimensional (2D) hybrid organic-inorganic halide perovskites incorporating for the first time 100% of a photoactive tetrazine derivative as the organic component. Namely, the use of a heterocyclic ring containing a nitrogen proportion imparts a unique electronic structure to the organic component, with the lowest energy optical absorption in the blue region. The present compound, a tetrazine, presents several resonances between the organic and inorganic components, both in terms of single particle electronic levels and exciton states, providing the ideal playground to discuss charge and energy transfer mechanisms at the organic/inorganic interface.

Cation Engineering for Resonant Energy Level Alignment in Two-Dimensional Lead Halide Perovskites.

Low-dimensional metal halide perovskites are being intensively investigated because of their higher stability and chemical versatility in comparison to their 3D counterparts. Unfortunately, this comes at the expense of the electronic and charge transport properties, limited by the reduced perovskite dimensionality. Cation engineering can be envisaged as a solution to tune and possibly further improve the material's optoelectronic properties.

First principles modeling of exciton-polaritons in polydiacetylene chains.

Exciton-polaritons in organic materials are hybrid states that result from the strong interaction of photons and the bound excitons that these materials host. Organic polaritons hold great interest for optoelectronic applications; however, progress toward this end has been impeded by the lack of a first principles approach that quantifies light-matter interactions in these systems, which would allow the formulation of molecular design rules. Here, we present a theoretical framework that combines first principles calculations for excitons with classical electrodynamics in order to quantify light-matter interactions.

Spatial Charge Separation as the Origin of Anomalous Stark Effect in Fluorous 2D Hybrid Perovskites.

2D hybrid perovskites (2DP) are versatile materials, whose electronic and optical properties can be tuned through the nature of the organic cations (even when those are seemingly electronically inert). Here, it is demonstrated that fluorination of the organic ligands yields glassy 2DP materials featuring long-lived correlated electron-hole pairs. Such states have a marked charge-transfer character, as revealed by the persistent Stark effect in the form of a second derivative in electroabsorption.

Organic Cations Protect Methylammonium Lead Iodide Perovskites against Small Exciton-Polaron Formation.

Working organic-inorganic lead halide perovskite-based devices are notoriously sensitive to surface and interface effects. Using a combination of density functional theory (DFT) and time-dependent DFT methods, we report a comprehensive study of the changes (with respect to the bulk) in geometric and electronic structures going on at the (001) surface of a (tetragonal phase) methylammonium lead iodide perovskite slab, in the dark and upon photoexcitation. The formation of a hydrogen bonding pattern between the -NH groups of the organic cations and the iodine atoms of the outer inorganic layout is found to critically contribute to the relative thermodynamic stability of slabs with varying surface compositions and terminations.

Fluorination of Organic Spacer Impacts on the Structural and Optical Response of 2D Perovskites.

Low-dimensional hybrid perovskites have triggered significant research interest due to their intrinsically tunable optoelectronic properties and technologically relevant material stability. In particular, the role of the organic spacer on the inherent structural and optical features in two-dimensional (2D) perovskites is paramount for material optimization. To obtain a deeper understanding of the relationship between spacers and the corresponding 2D perovskite film properties, we explore the influence of the partial substitution of hydrogen atoms by fluorine in an alkylammonium organic cation, resulting in (Lc)PbI and (Lf)PbI 2D perovskites, respectively.

Author Correction: Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites.

In the version of this Article originally published, the units of the Fig. 3a x axis were incorrectly given as meV. They should have been eV.

Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites.

Hybrid organic-inorganic semiconductors feature complex lattice dynamics due to the ionic character of the crystal and the softness arising from non-covalent bonds between molecular moieties and the inorganic network. Here we establish that such dynamic structural complexity in a prototypical two-dimensional lead iodide perovskite gives rise to the coexistence of diverse excitonic resonances, each with a distinct degree of polaronic character. By means of high-resolution resonant impulsive stimulated Raman spectroscopy, we identify vibrational wavepacket dynamics that evolve along different configurational coordinates for distinct excitons and photocarriers.

Tuning the Optoelectronic Properties of Two-Dimensional Hybrid Perovskite Semiconductors with Alkyl Chain Spacers.

Layered two-dimensional organo-metal halide perovskites are currently in the limelight, largely because their versatile chemical composition offers the promise of tunable photophysical properties. We report here on (time-dependent) density functional theory [(TD)DFT] calculations of alkyl-ammonium lead iodide perovskites, where significant changes in the electronic structure and optical properties are predicted when using long versus short alkyl chain spacers. The mismatch between the structural organization in the inorganic and organic layers is epitomized for dodecyl chains that adopt a supramolecular packing similar to that of polyethylene, at the cost of distorting the inorganic frame and, in turn, opening the electronic band gap.

Hot-Hole Cooling Controls the Initial Ultrafast Relaxation in Methylammonium Lead Iodide Perovskite.

Understanding the initial ultrafast excited state dynamics of methylammonium lead iodide (MAPI) perovskite is of vital importance to enable its fullest utilisation in optoelectronic devices and the design of improved materials. Here we have combined advanced measurements of the ultrafast photoluminescence from MAPI films up to 0.6 eV above the relaxed excited state with cutting-edge advanced non-adiabatic quantum dynamics simulations, to provide a powerful unique insight into the earliest time behaviour in MAPI.

Formation of Long-Lived Color Centers for Broadband Visible Light Emission in Low-Dimensional Layered Perovskites.

We investigate the origin of the broadband visible emission in layered hybrid lead-halide perovskites and its connection with structural and photophysical properties. We study ⟨001⟩ oriented thin films of hexylammonium (HA) lead iodide, (CHN)PbI, and dodecylammonium (DA) lead iodide, (CHN)PbI, by combining first-principles simulations with time-resolved photoluminescence, steady-state absorption and X-ray diffraction measurements on cooling from 300 to 4 K. Ultrafast transient absorption and photoluminescence measurements are used to track the formation and recombination of emissive states.

Vibrational Response of Methylammonium Lead Iodide: From Cation Dynamics to Phonon-Phonon Interactions.

The dynamic evolution of the vibrational interactions in the prototypical CH NH PbI was studied through a comprehensive experimental and theoretical investigation with a focus on the interactions between the organic cations and the inorganic cage. To date, no clear picture has emerged on the critical and fundamental interactions between the two perovskite components, despite the relevance of phonons to the electronic properties of several classes of perovskites. For the first time, we have monitored the IR and nonresonant Raman response in the broad frequency range 30-3400 cm and in the temperature interval 80-360 K.

Chlorine Incorporation in the CHNHPbI Perovskite: Small Concentration, Big Effect.

The role of chlorine doping in CHNHPbI represents an important open issue in the use of hybrid perovskites for photovoltaic applications. In particular, even if a positive role of chlorine doping on perovskite film formation and on material morphology has been demonstrated, an inherent positive effect on the electronic and photovoltaic properties cannot be excluded. Here we carried out periodic density functional theory and Car-Parrinello molecular dynamics simulations, going down to ∼1% doping, to investigate the effect of chlorine on CHNHPbI.

The Impact of the Crystallization Processes on the Structural and Optical Properties of Hybrid Perovskite Films for Photovoltaics.

We investigate the relationship between structural and optical properties of organo-lead mixed halide perovskite films as a function of the crystallization mechanism. For methylammonium lead tri-iodide, the organic cations rearrange within the inorganic cage, moving from crystals grown in a mesoporous scaffold to larger, oriented crystals grown on a flat substrate. This reduces the strain felt by the bonds forming the cage and affects the motion of the organic cation in it, influencing the electronic transition at the onset of the optical absorption spectrum of the semiconductor.

Photoinduced Reversible Structural Transformations in Free-Standing CH3NH3PbI3 Perovskite Films.

In the pursuit to better understand the mechanisms of perovskite solar cells we performed Raman and photoluminescence measurements of free-standing CH3NH3PbI3 films, comparing dark with working conditions. The films, grown on a glass substrate and sealed by a thin glass coverslip, were measured subsequent to dark and white-light pretreatments. The extremely slow changes we observe in both the Raman and photoluminescence cannot be regarded as electronic processes, which are much faster.

Ferroelectric Polarization of CH3NH3PbI3: A Detailed Study Based on Density Functional Theory and Symmetry Mode Analysis.

Ferroelectricity in halide perovskites currently represents a crucial issue, as it may have an important role for the enhancement of solar cells efficiency. Simulations of ferroelectric properties based on density functional theory are conceptually more demanding compared with "conventional" inorganic ferroelectrics due to the presence of both organic and inorganic components in the same compound. Here we present a detailed study focused on the prototypical CH3NH3PbI3 perovskite.

Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics.

The last two years have seen the unprecedentedly rapid emergence of a new class of solar cells, based on hybrid organic-inorganic halide perovskites. The success of this class of materials is due to their outstanding photoelectrochemical properties coupled to their low cost, mainly solution-based, fabrication techniques. Solution processed materials are however often characterized by an inherent flexible structure, which is hardly mapped into a single local minimum energy structure.