A universal ligand for lead coordination and tailored crystal growth in perovskite solar cells.

Chemical environment and precursor-coordinating molecular interactions within a perovskite precursor solution can lead to important implications in structural defects and crystallization kinetics of a perovskite film. Thus, the opto-electronic quality of such films can be boosted by carefully fine-tuning the coordination chemistry of perovskite precursors via controllable introduction of additives, capable of forming intermediate complexes. In this work, we employed a new type of ligand, namely 1-phenylguanidine (PGua), which coordinates strongly with the PbI2 complexes in the perovskite precursor, forming new intermediate species. These strong interactions effectively retard the perovskite crystallization process and form homogeneous films with enlarged grain sizes and reduced density of defects. In combination with an interfacial treatment, the resulted champion devices exhibit a 24.6% efficiency with outstanding operational stability. Unprecedently, PGua can be applied in various PSCs with different perovskite compositions and even in both configurations: n-i-p and p-i-n, highlighting the universality of this ligand.

Ligand-Induced Chirality in ClMBA2 SnI4 2D Perovskite.

Chiral perovskites possess a huge applicative potential in several areas of optoelectronics and spintronics. The development of novel lead-free perovskites with tunable properties is a key topic of current research. Herein, we report a novel lead-free chiral perovskite, namely (R/S-)ClMBA2 SnI4 (ClMBA=1-(4-chlorophenyl)ethanamine) and the corresponding racemic system. ClMBA2 SnI4 samples exhibit a low band gap (2.12 eV) together with broad emission extending in the red region of the spectrum (∼1.7 eV). Chirality transfer from the organic ligand induces chiroptical activity in the 465-530 nm range. Density functional theory calculations show a Rashba type band splitting for the chiral samples and no band splitting for the racemic isomer. Self-trapped exciton formation is at the origin of the large Stokes shift in the emission. Careful correlation with analogous lead and lead-free 2D chiral perovskites confirms the role of the symmetry-breaking distortions in the inorganic layers associated with the ligands as the source of the observed chiroptical properties providing also preliminary structure-property correlation in 2D chiral perovskites.

Tuning Structure and Excitonic Properties of 2D Ruddlesden-Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations.

The compositional tunability of 2D metal halide perovskites enables exploration of diverse semiconducting materials with different structural features. However, rationally tuning the 2D perovskite structures to target physical properties for specific applications remains challenging, especially for lead-free perovskites. Here, we study the effect of the interplay of the B-site (Ge, Sn, and Pb), A-site (cesium, methylammonium, and formamidinium), and spacer cations on the structure and optical properties of a new series of 2D Ruddlesden-Popper perovskites using the previously unreported spacer cation 4-bromo-2-fluorobenzylammonium (4Br2FBZ). We report eight new crystal structures and study the consequence of varying the B-site (Pb, Sn, Ge) and dimension (n = 1, 2, vs 3D). Dimension strongly influences local distortion and structural symmetry, and the increased octahedral tilting and lone pair effects in Ge perovskites lead to a polar n = 2 perovskite that exhibits second harmonic generation, (4Br2FBZ)2(Cs)Ge2I7. In contrast, the analogous Sn and Pb perovskites remain centrosymmetric, but the B-site metal influences the photoluminescence properties. The Pb perovskites exhibit broad, defect-mediated emission at low temperature, whereas the Sn perovskites show purely excitonic emission over the entire temperature range, but the carrier recombination dynamics depend on dimensionality and dark excitonic states. Wholistic understanding of these differences that arise based on cations and dimensionality can guide the rational materials design of 2D perovskites for targeting physical properties for optoelectronic applications based on the interplay of cations and the connectivity of the inorganic framework.

Synergistic Role of Water and Oxygen Leads to Degradation in Formamidinium-Based Halide Perovskites.

Mixed-cation metal halide perovskites have shown remarkable progress in photovoltaic applications with high power conversion efficiencies. However, to achieve large-scale deployment of this technology, efficiencies must be complemented by long-term durability. The latter is limited by external factors, such as exposure to humidity and air, which lead to the rapid degradation of the perovskite materials and devices. In this work, we study the mechanisms causing Cs and formamidinium (FA)-based halide perovskite phase transformations and stabilization during moisture and air exposure. We use in situ X-ray scattering, X-ray photoelectron spectroscopy, and first-principles calculations to study these chemical interactions and their effects on structure. We unravel a surface reaction pathway involving the dissolution of FAI by water and iodide oxidation by oxygen, driving the Cs/FA ratio into thermodynamically unstable regions, leading to undesirable phase transformations. This work demonstrates the interplay of bulk phase transformations with surface chemical reactions, providing a detailed understanding of the degradation mechanism and strategies for designing durable and efficient perovskite materials.

Origin of Broad Emission Induced by Rigid Aromatic Ditopic Cations in Low-Dimensional Metal Halide Perovskites.

The development of broadband emitters based on metal halide perovskites (MHPs) requires the elucidation of structure-emission property correlations. Herein, we report a combined experimental and theoretical study on a series of novel low-dimensional lead chloride perovskites, including ditopic aromatic cations. Synthesized lead chloride perovskites and their bromide analogues show both narrow and broad photoluminescence emission properties as a function of their cation and halide nature. Structural analysis shows a correlation between the rigidity of the ditopic cations and the lead halide octahedral distortions. Density functional theory calculations reveal, in turn, the pivotal role of octahedral distortions in the formation of self-trapped excitons, which are responsible for the insurgence of broad emission and large Stokes shifts together with a contribution of halide vacancies. For the considered MHP series, the use of conventional octahedral distortion parameters allows us to nicely describe the trend of emission properties, thus providing a solid guide for further materials design.

Increased CO2 Affinity and Adsorption Selectivity in MOF-801 Fluorinated Analogues.

The novel ZrIV-based perfluorinated metal-organic framework (PF-MOF) [Zr6O4(OH)4(TFS)6] (ZrTFS) was prepared under solvent-free conditions using the commercially available tetrafluorosuccinic acid (H2TFS) as a bridging ditopic linker. Since H2TFS can be seen as the fully aliphatic and perfluorinated C4 analogue of fumaric acid, ZrTFS was found to be isoreticular to zirconium fumarate (MOF-801). The structure of ZrTFS was solved and refined from X-ray powder diffraction data. Despite this analogy, the gas adsorption capacity of ZrTFS is much lower than that of MOF-801; in the former, the presence of bulky fluorine atoms causes a considerable window size reduction. To have PF-MOFs with more accessible porosity, postsynthetic exchange (PSE) reactions on (defective) MOF-801 suspended in H2TFS aqueous solutions were carried out. Despite the different H2TFS concentrations used in the PSE process, the exchanges yielded two mixed-linker materials of similar minimal formulae [Zr6O4(µ3-OH)4(µ1-OH)2.08(H2O)2.08(FUM)4.04(HTFS)1.84] (PF-MOF1) and [Zr6O4(µ3-OH)4(µ1-OH)1.83(H2O)1.83(FUM)4.04(HTFS)2.09] (PF-MOF2) (FUM2- = fumarate), where the perfluorinated linker was found to fully replace the capping acetate in the defective sites of pristine MOF-801. CO2 and N2 adsorption isotherms collected on all samples reveal that both CO2 thermodynamic affinity (isosteric heat of adsorption at zero coverage, Qst) and CO2/N2 adsorption selectivity increase with the amount of incorporated TFS2-, reaching the maximum values of 30 kJ mol-1 and 41 (IAST), respectively, in PF-MOF2. This confirms the beneficial effect coming from the introduction of fluorinated linkers in MOFs on their CO2 adsorption ability. Finally, solid-state density functional theory calculations were carried out to cast light on the structural features and on the thermodynamics of CO2 adsorption in MOF-801 and ZrTFS. Due to the difficulties in modeling a defective MOF, an intermediate structure containing both linkers in the framework was also designed. In this structure, the preferential CO2 adsorption site is the tetrahedral pore in the "UiO-66-like" structure. The extra energy stabilization stems from a hydrogen bond interaction between CO2 and a hydroxyl group on the inorganic cluster.

Local Temporal Acceleration Scheme to Couple Transport and Reaction Dynamics in Kinetic Monte Carlo Models of Electrochemical Systems.

Kinetic Monte Carlo (kMC) simulations are a well-established tool for investigating the operation of electrochemical systems. Standard kMC algorithms become unfeasible in the presence of processes on vastly different time scales. In electrochemical systems, such time scale disparities often arise between fast transport processes and slow electrochemical reactions. A promising approach to overcome time scale disparities in kMC models is given by temporal acceleration schemes. In this work, we present a local temporal acceleration scheme to bridge the time scale disparity between fast transport and slow reaction dynamics. We combine the superbasin concept with a local, particle-based criterion for the quasi-equilibrium detection and a partitioning of transitions and particles in the system into process chains. Scaling of entire quasi-equilibrated process chains considerably reduces the computational effort without disturbing the relative dynamics of transitions within a process chain. The methodology is outlined for a hybrid organic-aqueous electrolyte device which links fast electronic processes in an organic semiconductor with slow reduction reactions at its interface to the electrolyte. Our approach captures local inhomogeneities such that local physical quantities can be reproduced accurately. Additionally, we show that previous accelerated superbasin algorithms are limited by the presence of spatially varying time scale disparities. Our algorithm achieves an acceleration of several orders of magnitude providing a serious alternative to replace existing multiscale models by stand-alone kMC simulations.

Stability of Tin- versus Lead-Halide Perovskites: Ab Initio Molecular Dynamics Simulations of Perovskite/Water Interfaces.

Tin-halide perovskites (THPs) have emerged as promising lead-free perovskites for photovoltaics and photocatalysis applications but still fall short in terms of stability and efficiency with respect to their lead-based counterpart. A detailed understanding of the degradation mechanism of THPs in a water environment is missing. This Letter presents ab initio molecular dynamics (AIMD) simulations to unravel atomistic details of THP/water interfaces comparing methylammonium tin iodide, MASnI3, with the lead-based MAPbI3. Our results reveal facile solvation of surface tin-iodine bonds in MASnI3, while MAPbI3 remains more robust to degradation despite a larger amount of adsorbed water molecules. Additional AIMD simulations on dimethylammonium tin bromide, DMASnBr3, investigate the origins of their unprecedented water stability. Our results indicate the presence of amorphous surface layers of hydrated zero-dimensional SnBr3 complexes which may protect the inner structure from degradation and explain their success as photocatalysts. We believe that the atomistic details of the mechanisms affecting THP (in-)stability may inspire new strategies to stabilize THPs.

First-Principles Molecular Dynamics in Metal-Halide Perovskites: Contrasting Generalized Gradient Approximation and Hybrid Functionals.

First-principles molecular dynamics (FPMD) represents a valuable tool to probe dynamical properties of metal-halide perovskites (MHPs) which are key to their success in optoelectronic devices. Most FPMD studies rely on generalized gradient approximation (GGA) functionals for computational efficiency matters, while hybrid functionals, although computationally demanding, are usually needed to accurately describe structural and electronic properties of MHPs. This Letter reports FPMD simulations on CsPbI3 based on the hybrid PBE0 functional. Our results demonstrate that PBE0 leads to lattice parameters and phonon modes in excellent agreement with experimental data, while GGA results overestimate the lattice parameter and the electronic band gap and underestimate the phonon energies. Our FPMD results also shed light on anharmonic effects and double-well instabilities in the octahedral tilting, highlighting a lowered free energy barrier for PBE0 and farther separated potential wells. Our results suggest that hybrid functionals are required to accurately describe crystal structure, lattice dynamics, and anharmonicity in MHPs.

Nonequilibrium Thermodynamics of Charge Separation in Organic Solar Cells.

This work presents a novel theoretical description of the nonequilibrium thermodynamics of charge separation in organic solar cells (OSCs). Using stochastic thermodynamics, we take realistic state populations derived from the phonon-assisted dynamics of electron-hole pairs within photoexcited organic bilayers to connect the kinetics with the free energy profile of charge separation. Hereby, we quantify for the first time the difference between nonequilibrium and equilibrium free energy profile. We analyze the impact of energetic disorder and delocalization on free energy, average energy, and entropy. For a high disorder, the free energy profile is well-described as equilibrated. We observe significant deviations from equilibrium for delocalized electron-hole pairs at a small disorder, implying that charge separation in efficient OSCs proceeds via a cold but nonequilibrated pathway. Both a large Gibbs entropy and large initial electron-hole distance provide an efficient charge separation, while a decrease in the free energy barrier does not necessarily enhance charge separation.

Stepping Out of Equilibrium: The Quest for Understanding the Role of Non-Equilibrium (Thermo-)Dynamics in Electronic and Electrochemical Processes.

This editorial aims to interest researchers and inspire novel research on the topic of non-equilibrium Thermodynamics and Monte Carlo for Electronic and Electrochemical Processes. We present a brief outline on recent progress and challenges in the study of non-equilibrium dynamics and thermodynamics using numerical Monte Carlo simulations. The aim of this special issue is to collect recent advances and novel techniques of Monte Carlo methods to study non-equilibrium electronic and electrochemical processes at the nanoscale.

Acceleration scheme for particle transport in kinetic Monte Carlo methods.

Kinetic Monte Carlo (kMC) simulations are frequently used to study (electro-)chemical processes within science and engineering. kMC methods provide insight into the interplay of stochastic processes and can link atomistic material properties with macroscopic characteristics. Significant problems concerning the computational demand arise if processes with large time disparities are competing. Acceleration algorithms are required to make slow processes accessible. Especially, the accelerated superbasin kMC (AS-kMC) scheme has been frequently applied within chemical reaction networks. For larger systems, the computational overhead of the AS-kMC is significant as the computation of the superbasins is done during runtime and comes with the need for large databases. Here, we propose a novel acceleration scheme for diffusion and transport processes within kMC simulations. Critical superbasins are detected during the system initialization. Scaling factors for the critical rates within the superbasins, as well as a lower bound for the number of sightings, are derived. Our algorithm exceeds the AS-kMC in the required simulation time, which we demonstrate with a 1D-chain example. In addition, we apply the acceleration scheme to study the time-of-flight (TOF) of charge carriers within organic semiconductors. In this material class, time disparities arise due to a significant spread of transition rates. The acceleration scheme allows a significant acceleration up to a factor of 65 while keeping the error of the TOF values negligible. The computational overhead is negligible, as all superbasins only need to be computed once.

TAF-ChIP: an ultra-low input approach for genome-wide chromatin immunoprecipitation assay.

Chromatin immunoprecipitation (ChIP) followed by next generation sequencing (ChIP-Seq) is a powerful technique to study transcriptional regulation. However, the requirement of millions of cells to generate results with high signal-to-noise ratio precludes it in the study of small cell populations. Here, we present a tagmentation-assisted fragmentation ChIP (TAF-ChIP) and sequencing method to generate high-quality histone profiles from low cell numbers. The data obtained from the TAF-ChIP approach are amenable to standard tools for ChIP-Seq analysis, owing to its high signal-to-noise ratio. The epigenetic profiles from TAF-ChIP approach showed high agreement with conventional ChIP-Seq datasets, thereby underlining the utility of this approach.

Charge carrier mobility of disordered organic semiconductors with correlated energetic and spatial disorder.

Low charge carrier mobility is one key factor limiting the performance and applicability of devices based on organic semiconductors. Theoretical studies on mobility using the kinetic Monte Carlo or master equation are mainly based on a Gaussian energetic disorder and regular cubic lattices. The dependence of mobility on the electric field, temperature and charge carrier density is well studied for the Gaussian disorder model. In this work, we investigate the influence of spatially correlated site energies and spatial disorder in the lattice sites on the mobility using kinetic Monte Carlo simulations. Our analysis is based on both a regular cubic and a non-cubic Voronoi lattice. The latter is used to include spatial disorder in order to study its influence on the mobility for amorphous organic materials. Our results show that charge carrier mobility is strongly influenced by correlations in the site energies. Strong correlations even invert the field dependence of the mobility as observed experimentally in semi-crystalline polymers such as P3HT. Evaluation of local currents between localized states reveals the formation of current filaments with increasing correlation. Furthermore, the influence of the electric field and the energy landscape on the transport energy is studied by evaluation of active sites. A strong correlation between the transport energy, filaments in the local currents and the charge carrier mobility is observed. Our studies on the spatial disorder model do not indicate an inversion of the field dependence as observed by other researchers. The negative field-dependence in semi-crystalline materials may be explained by a higher correlation in the site energies as shown in a strongly correlated energetic landscape.