Two-Dimensional Moiré Polaronic Electron Crystals.

Two-dimensional moiré materials have emerged as the most versatile platform for realizing quantum phases of electrons. Here, we explore the stability origins of correlated states in WSe_{2}/WS_{2} moiré superlattices. We find that ultrafast electronic excitation leads to partial melting of the Mott states on timescales 5 times longer than predictions from the charge hopping integrals and that the melting rates are thermally activated, with activation energies of 18±3 and 13±2 meV for the one- and two-hole Mott states, respectively, suggesting significant electron-phonon coupling. A density functional theory calculation of the one-hole Mott state confirms polaron formation and yields a hole-polaron binding energy of 16 meV. These findings reveal a close interplay of electron-electron and electron-phonon interactions in stabilizing the polaronic Mott insulators at transition metal dichalcogenide moiré interfaces.

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.

Unraveling Atomic Contributions to the London Dispersion Energy: Insights into Molecular Recognition and Reactivity.

We present a general framework that enables quantification with atomic resolution of the overall London dispersion energy, which can be readily integrated with currently available energy decomposition schemes. This approach can be used to determine the contribution of individual atoms and functional groups to molecular recognition, conformational preferences, molecular stability, and reactivity. Its efficacy across diverse realms of molecular chemistry and biology is demonstrated with application to molecular balances in solution, asymmetric organocatalytic transformations, and a subcomplex of the F1FO ATP synthase.

Multifunctional sulfonium-based treatment for perovskite solar cells with less than 1% efficiency loss over 4,500-h operational stability tests.

The stabilization of grain boundaries and surfaces of the perovskite layer is critical to extend the durability of perovskite solar cells. Here we introduced a sulfonium-based molecule, dimethylphenethylsulfonium iodide (DMPESI), for the post-deposition treatment of formamidinium lead iodide perovskite films. The treated films show improved stability upon light soaking and remains in the black α phase after two years ageing under ambient condition without encapsulation. The DMPESI-treated perovskite solar cells show less than 1% performance loss after more than 4,500 h at maximum power point tracking, yielding a theoretical T80 of over nine years under continuous 1-sun illumination. The solar cells also display less than 5% power conversion efficiency drops under various ageing conditions, including 100 thermal cycles between 25 °C and 85 °C and an 1,050-h damp heat test.

Harnessing the electronic structure of active metals to lower the overpotential of the electrocatalytic oxygen evolution reaction.

Despite substantial advancements in the field of the electrocatalytic oxygen evolution reaction (OER), the efficiency of earth-abundant electrocatalysts remains far from ideal. The difficulty stems from the complex nature of the catalytic system, which limits our fundamental understanding of the process and thus the possibility of a rational improvement of performance. Herein, we shed light on the role played by the tunable 3d configuration of the metal centers in determining the OER catalytic activity by combining electrochemical and spectroscopic measurements with an experimentally validated computational protocol. One-dimensional coordination polymers based on Fe, Co and Ni held together by an oxonato linker were selected as a case study because of their well-defined electronic and geometric structure in the active site, which can be straightforwardly correlated with their catalytic activity. Novel heterobimetallic coordination polymers were also considered, in order to shed light on the cooperativity effects of different metals. Our results demonstrate the fundamental importance of electronic structure effects such as metal spin and oxidation state evolutions along the reaction profile to modulate ligand binding energies and increase catalyst efficiency. We demonstrated that these effects could in principle be exploited to reduce the overpotential of the electrocatalytic OER below its theoretical limit, and we provide basic principles for the development of coordination polymers with a tailored electronic structure and activity.

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.

How Photogenerated I2 Induces I-Rich Phase Formation in Lead Mixed Halide Perovskites.

Bandgap tunability of lead mixed halide perovskites (LMHPs) is a crucial characteristic for versatile optoelectronic applications. Nevertheless, LMHPs show the formation of iodide-rich (I-rich) phase under illumination, which destabilizes the semiconductor bandgap and impedes their exploitation. Here, it is shown that how I2 , photogenerated upon charge carrier trapping at iodine interstitials in LMHPs, can promote the formation of I-rich phase. I2 can react with bromide (Br- ) in the perovskite to form a trihalide ion I2 Br- (Iδ- -Iδ+ -Brδ- ), whose negatively charged iodide (Iδ- ) can further exchange with another lattice Br- to form the I-rich phase. Importantly, it is observed that the effectiveness of the process is dependent on the overall stability of the crystalline perovskite structure. Therefore, the bandgap instability in LMHPs is governed by two factors, i.e., the density of native defects leading to I2 production and the Br- binding strength within the crystalline unit. Eventually, this study provides rules for the design of chemical composition in LMHPs to reach their full potential for optoelectronic devices.

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.

How Halide Alloying Influences the Optoelectronic Quality in Tin-Halide Perovskite Solar Absorbers.

Halide alloying in tin-based perovskites allows for photostable bandgap tuning between 1.3 and 2.2 eV. Here, we elucidate how the band edge energetics and associated defect activity impact the optoelectronic properties of this class of materials. We find that by increasing the bromide:iodide ratio, a simultaneous destabilization of acceptor defects (tin vacancies and iodine interstitials) and stabilization of donor defects (iodine vacancies and tin interstitials) occurs, with strong changes arising for Br contents exceeding 50%. This translates into a decreased doping which is, however, accompanied by a higher density of nonradiative recombination channels. Films with high Br content show a high degree of disorder and trap state densities, with the best optoelectronic quality being found for Br contents of around 33%. These observations match the open circuit voltage trend of tin-based mixed halide perovskite solar cells, supporting the relevance of optoelectronic properties and chemistry of defects to optimize wide-bandgap tin perovskite devices.

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.

Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System.

Finding stable analogues of three-dimensional (3D) lead halide perovskites has motivated the exploration of an ever-expanding repertoire of two-dimensional (2D) counterparts. However, the bandgap and exciton binding energy in these 2D systems are generally considerably higher than those in 3D analogues due to size and dielectric confinement. Such quantum confinements are most prominently manifested in the extreme 2D realization in (A)mPbI4 (m = 1 or 2) series of compounds with a single inorganic layer repeat unit. Here, we explore a new A-site cation, 4,4'-azopyridine (APD), whose size and hydrogen bonding properties endow the corresponding (APD)PbI4 2D compound with the lowest bandgap and exciton binding energy of all such compounds, 2.19 eV and 48 meV, respectively. (APD)PbI4 presents the first example of the ideal Pb-I-Pb bond angle of 180°, maximizing the valence and conduction bandwidths and minimizing the electron and hole effective masses. These effects coupled with a significant increase in the dielectric constant provide an explanation for the unique bandgap and exciton binding energies in this system. Our theoretical results further reveal that the requirement of optimizing the hydrogen bonding interactions between the organic and the inorganic units provides the driving force for achieving the structural uniqueness and the associated optoelectronic properties in this system. Our preliminary investigations in characterizing photovoltaic solar cells in the presence of APD show encouraging improvements in performances and stability.

Air- and water-stable and photocatalytically active germanium-based 2D perovskites by organic spacer engineering.

There is increasing interest in the role of metal halide perovskites for heterogeneous catalysis. Here, we report a Ge-based 2D perovskite material that shows intrinsic water stability realized through organic cation engineering. Incorporating 4-phenylbenzilammonium (PhBz) we demonstrate, by means of extended experimental and computational results, that PhBz2GeBr4 and PhBz2GeI4 can achieve relevant air and water stability. The creation of composites embedding graphitic carbon nitride (g-C3N4) allows a proof of concept for light-induced hydrogen evolution in an aqueous environment by 2D Ge-based perovskites thanks to the effective charge transfer at the heterojunction between the two semiconductors.

Modeling the Interaction of Coronavirus Membrane Phospholipids with Photocatalitically Active Titanium Dioxide.

The outbreak of viral infectious diseases urges airborne droplet and surface disinfection strategies, which may rely on photocatalytic semiconductors. A lipid bilayer membrane generally encloses coronaviruses and promotes the anchoring on the semiconductor surface, where, upon photon absorption, electron-hole pairs are produced, which can react with adsorbed oxygen-containing species and lead to the formation of reactive oxygen species (ROSs). The photogenerated ROSs may support the disruptive oxidation of the lipidic membrane and pathogen death. Density functional theory calculations are employed to investigate adsorption modes, energetics, and electronic structure of a reference phospholipid on anatase TiO2 nanoparticles. The phospholipid covalently bound on TiO2, engaging a stronger adsorption on the (101) than on the (001) surface. The energetically most stable structure involves the formation of four covalent bonds through phosphate and carbonyl oxygen atoms. The adsorbates show a reduction of the band gap compared with standalone TiO2, suggesting a significant interfacial coupling.

Defect Engineering to Achieve Photostable Wide Bandgap Metal Halide Perovskites.

Bandgap tuning is a crucial characteristic of metal-halide perovskites, with benchmark lead-iodide compounds having a bandgap of 1.6 eV. To increase the bandgap up to 2.0 eV, a straightforward strategy is to partially substitute iodide with bromide in so-called mixed-halide lead perovskites. Such compounds are prone, however, to light-induced halide segregation resulting in bandgap instability, which limits their application in tandem solar cells and a variety of optoelectronic devices. Crystallinity improvement and surface passivation strategies can effectively slow down, but not completely stop, such light-induced instability. Here we identify the defects and the intragap electronic states that trigger the material transformation and bandgap shift. Based on such knowledge, we engineer the perovskite band edge energetics by replacing lead with tin and radically deactivate the photoactivity of such defects. This leads to metal halide perovskites with a photostable bandgap over a wide spectral range and associated solar cells with photostable open circuit voltages.

Cubic or Not Cubic? Combined Experimental and Computational Investigation of the Short-Range Order of Tin Halide Perovskites.

Tin-based metal halide perovskites with a composition of ASnX3 (where A= MA or FA and X = I or Br) have been investigated by means of X-ray total scattering techniques coupled to pair distribution function (PDF) analysis. These studies revealed that that none of the four perovskites has a cubic symmetry at the local scale and that a degree of increasing distortion is always present, in particular when the cation size is increased, i.e., from MA to FA, and the hardness of the anion is increased, i.e., from Br- to I-. Electronic structure calculations provided good agreement with experimental band gaps for the four perovskites when local dynamical distortions were included in the calculations. The averaged structure obtained from molecular dynamics simulations was consistent with experimental local structures determined via X-ray PDF, thus highlighting the robustness of computational modeling and strengthening the correlation between experimental and computational results.

Solvent dependent iodide oxidation in metal-halide perovskite precursor solutions.

Solar cell absorbing layers made of metal-halide perovskites (MHPs) are usually deposited from solution phase precursors, which is one of the reasons why these materials received huge research attention in the last few years. A detailed knowledge of the solution chemistry is critical to understand the formation of MHP thin films and thus to control their optoelectronic properties and the reproducibility issues that usually affect their synthesis. In this regard, the concentration of triiodide, I3-, is one factor known to have an influence on regulating important aspects such as the particle size in the solution and the defect concentration in the film. In this study, we highlight an underestimated source of I3-, namely the iodide salt solutions ubiquitously employed in MHP synthetic routes, which not only lead to the formation of I3- but also detracts available I- for the MHP synthesis, thus establishing under-stoichiometric conditions. Particularly, we show how the oxidation of I- to I3- changes in time with both the iodide salt counter-cation (K+, CH3NH3+) and the used solvent, meaning that variable quantities of I3- are found depending on the synthesis conditions, with enhanced oxidation found in the γ-butyrolactone (GBL) solvent. Though these differences are generally small, we shed light on a hidden and ever-present reaction which is likely to be related to the overall processing quality of MHP thin films.

The Origin of Broad Emission in ⟨100⟩ Two-Dimensional Perovskites: Extrinsic vs Intrinsic Processes.

2D metal halide perovskites can show narrow and broad emission bands (BEs), and the latter's origin is hotly debated. A widespread opinion assigns BEs to the recombination of intrinsic self-trapped excitons (STEs), whereas recent studies indicate they can have an extrinsic defect-related origin. Here, we carry out a combined experimental-computational study into the microscopic origin of BEs for a series of prototypical phenylethylammonium-based 2D perovskites, comprising different metals (Pb, Sn) and halides (I, Br, Cl). Photoluminescence spectroscopy reveals that all of the compounds exhibit BEs. Where not observable at room temperature, the BE signature emerges upon cooling. By means of DFT calculations, we demonstrate that emission from halide vacancies is compatible with the experimentally observed features. Emission from STEs may only contribute to the BE in the wide-band-gap Br- and Cl-based compounds. Our work paves the way toward a complete understanding of broad emission bands in halide perovskites that will facilitate the fabrication of efficient narrow and white light emitting devices.

Photoluminescence Intensity Enhancement in Tin Halide Perovskites.

The prevalence of background hole doping in tin halide perovskites usually dominates their recombination dynamics. The addition of excess Sn halide source to the precursor solution is the most frequently used approach to reduce the hole doping and reveals photo-carrier dynamics related to defects activity. This study presents an experimental and theoretical investigation on defects under light irradiation in tin halide perovskites by combining measurements of photoluminescence with first principles computational modeling. It finds that tin perovskite thin films prepared with an excess of Sn halide sources exhibit an enhancement of the photoluminescence intensity over time under continuous excitation in inert atmosphere. The authors propose a model in which light irradiation promotes the annihilation of VSn 2- /Sni 2+ Frenkel pairs, reducing the deep carrier trapping centers associated with such defect and increasing the radiative recombination. Importantly, these observations can be traced in the open-circuit voltage dynamics of tin-based halide perovskite solar cells, implying the relevance of controlling the Sn photochemistry to stabilize tin perovskite devices.

Modeling titanium dioxide nanostructures for photocatalysis and photovoltaics.

Heterogenous photocatalysis is regarded as a holy grail in relation to the energy and environmental issues with which our society is currently struggling. In this context, the characterization of titanium dioxide nanostructures and the relationships between structural/electronic parameters and chemical/physical-chemical properties is a primary target, whose achievement is in high demand. Theoretical simulations can strongly support experiments to reach this goal. While the bulk and surface properties of TiO2 materials are quite well understood, the field of nanostructures still presents a few unexplored areas. Here we consider possible approaches for the modeling of reduced and extended TiO2 nanostructures, and we review the main outcomes of the investigation of the structural, electronic, and optical properties of TiO2 nanoparticles and their relationships with the size, morphology, and shape of the particles. Further investigations are highly desired to fill the gaps still remaining and to allow improvements in the efficiencies of these materials for photocatalytic and photovoltaic applications.