Ruddlesden-Popper Phase Research Articles

Separation of 2D Ruddlesden-Popper phase methylammonium lead bromide perovskite layers through hydrogen bonding of 5-aminovaleric acid organic spacer cations by colloidal solution method

2D Ruddlesden-Popper (RP) phase methylammonium lead bromide perovskites with different layers (n = 1, 2, and 3) were successfully synthesized through hydrogen bonding between 5-aminovaleric acid (5-AVA) organic cations using colloidal solution method. XRD patterns confirmed the formation of 2D perovskites with their layer thickness. Further, UV–vis absorption and PL spectra revealed the tuning of optical properties could be achieved by changing the layer thickness of 2D perovskites. The outcomes of our research might assist in the development of various layered 2D perovskites with carboxylic group-based organic spacers that may find applications in the field of optoelectronics.

Iterative cluster expansion approach for predicting the structure evolution of mixed Ruddelsden-Popper oxides La2−xSrxNi1−yFeyO4±δ

Layered perovskites viz. Ruddlesden-Popper (RP) compounds have attracted a significant research interest lately due to their superior electrocatalytic activities, on top of their rich physics. Although the versatility of their compositional space is the key to tune their stability and applicability, its complexity also makes the understanding and design of new functional RP-based materials difficult. Herein by parameterizing a cluster expansion model Hamiltonian with density-functional inputs, we have successfully scanned over the complex configurational space of an RP phase, taking ${\mathrm{La}}_{2\ensuremath{-}x}{\mathrm{Sr}}_{x}{\mathrm{Ni}}_{1\ensuremath{-}y}{\mathrm{Fe}}_{y}{\mathrm{O}}_{4\ifmmode\pm\else\textpm\fi{}\ensuremath{\delta}}$ as an example. This surrogate model is then used to predict the energies of unknown compositions and performing Metropolis Monte Carlo sampling for finding the ground-state structures. By analyzing these stable configurations at different $x, y$'s, and $\ensuremath{\delta}$=0, 0.125, we found that apical vacancies in the rock-salt layer are more favorable due to lesser steric forces but changes in $A$-site oxidation state due to Sr substitution can facilitate equatorial O-vacancy formation even in the perovskite layers. Our results uncover the structural evolution of RP oxides with increasing $A$-site (Sr) and $B$-site (Fe) substitutions. We find that a critical Sr concentration is required to stabilize Fe in these systems. With increasing Sr concentration, the $A$-site charge state changes gradually from ${\mathrm{La}}^{+3}$ to ${\mathrm{Sr}}^{+2}$, which facilitates both O-vacancy formation and stabilization of the $B$-site dopants. The findings further highlight the effects of configurational changes for the same composition on electronic structure. Thus, our work clearly demonstrates the importance of exploring configurational space of these complex oxides when using electronic-structure features as descriptors of their catalytic and other functional properties.

Computational and Experimental Study on the Combined Sulfur and Chromium Poisoning Mechanism of LSM, LSCF and LNO Cathodes

Perovskites (La,Sr)MnO3 (LSM) and (La,Sr)(Co,Fe)O3 (LSCF) phases and Ruddlesden-Popper phase La2NiO4 (LNO) as solid oxide fuel cell (SOFC) cathodes, have been used due to its high efficiency and low emissions. To further understand the long-term degradation mechanism of the LSM, LSCF, and LNO phase in SO2 and Cr vapor gas impurities, they were prepared, sintered, and heat-treated at 800, 900, and 1000 ℃ in the sulfur, chromium, and water vapor-containing atmospheres, respectively. Later, XRD, SEM, and TEM techniques were applied to the samples, and corresponding simulations were made by the CALPHAD approach based on the same experimental conditions to verify the formation of the detrimental secondary phases. Results showed good agreement among the predictions and experiments. More importantly, extensive simulations were conducted under different conditions (temperature, the partial pressure of oxygen, and impurities) to understand the long-term degradation mechanism and optimize the operating conditions.

Oxygen Transport in Higher-Order Ruddlesden-Popper Phase Materials

A series of Ruddlesden-Popper phase materials – La3PrNi3O10- δ, La2Pr2Ni3O10-δ and LaPr3Ni3O10- δ – were synthesised and investigated by neutron powder diffraction to understand the oxygen defect structure. The thermal expansion coefficient was calculated for all compositions and was found to be in the range of 13.0 - 13.4 × 10-6 ˚C-1, which is compatible with the commonly used electrolyte materials for solid oxide fuel cells. A weak preference for Pr occupying the M(2) site in the rocksalt layer was also observed. The majority of the oxygen vacancies were confined to the perovskite layers with a particular preference for O(1) and O(5) sites at high temperatures observed by neutron diffraction measurements. Further, a preference for a curved oxygen transport pathway around the NiO6 octahedra was observed which agrees with the published literature for these materials.

Li+ ion exchange in H2SrTa2O7 via low temperature acid/base reactions

Layered materials form a wide range of technologically important ceramics. Within the class of layered materials, ion-exchangeable tantalates have shown great promise. However, the majority of ion exchange methods require large molar excesses of reagents, high temperatures, and by-products or undesired second phases that have to be removed in subsequent reaction steps. Here we show how direct reaction of H2SrTa2O7 with varying quantities of LiOH.H2O at room temperature can exchange protons for Li+. This process does not form a continuous series such as that observed in H2-xLixLa2Ti3O10, instead forming LiHSrTa2O7 balanced with either unreacted H2SrTa2O7 or LiOH.H2O depending on the initial ratio of H2SrTa2O7 to LiOH.H2O. When H2SrTa2O7 is mixed at room temperature with less than one equivalent of LiOH.H2O it reacts to produce a mixture of H2SrTa2O7 and LiHSrTa2O7. Mixing equimolar amounts of H2SrTa2O7 and LiOH.H2O produces a single phase of LiHSrTa2O7. Room temperature mixing with x LiOH.H2O (1 < x < 2) followed by heating to 120 °C gives a two-phase product mixture of LiHSrTa2O7 and Li2SrTa2O7 and a single phase Li2SrTa2O7 from a reaction with x = 2.LiHSrTa2O7 can be further dehydrated at 360 °C to form the defect layered perovskite, ☐LiSrTa2O6.5. Materials with Li+ and vacancies on the same crystallographic site often show fast ion conduction but controllable synthesis has previously proved challenging. The synthesis and degree of exchange is investigated using X-ray powder diffraction data, thermogravimetric analysis and the ionic mobility assessed via a.c. impedance spectroscopy. As use of LiOH.H2O has now been shown to directly control ion exchange in both n = 1 and n = 3 (ideal) and n = 2 (distorted) Ruddlesden Popper phases the application of this methodology generally to layered materials is discussed.

Oxygen exchange and transport properties of the first-order Ruddlesden-Popper phase La2Ni0.9Co0.1O4+δ

The rare earth nickelate La2Ni0.9Co0.1O4+δ (LNCO) was synthesized via the citrate/EDTA method. X-ray powder diffraction confirmed that the material is single-phase and crystallizes in the orthorhombic K2NiF4-type structure. In-situ dc-conductivity and conductivity relaxation measurements on a bar-shaped sample were applied to determine the electronic conductivity as well as the chemical surface exchange coefficient and chemical diffusion coefficient of oxygen from 600 °C to 850 °C and 0.01 ≤ pO2 / bar ≤ 0.1. The results indicate that substitution of nickel with cobalt in La2Ni0.9Co0.1O4+δ leads to significantly higher values of the surface exchange coefficient compared to La2NiO4+δ, while the electronic conductivity is somewhat reduced. The oxygen non-stoichiometry of LNCO was studied by thermogravimetry in the same temperature and oxygen partial pressure range. The measured thermal expansion coefficients of LNCO fit well with those of common solid electrolytes such as GDC and YSZ. Self-diffusion coefficients of oxygen and ionic conductivities were calculated from the experimentally determined diffusivities and the thermodynamic factor of oxygen by using the Nernst-Einstein relation. The results indicate that LNCO offers an attractive option for application as air electrode in solid oxide cells.

Growth and phase transition of Sr3Zr2O7 single crystals

The melting behavior of Ruddlesden-Popper type hybrid improper ferroelectric Sr3Zr2O7 phase in the ZrO2–SrO pseudo-binary system was investigated, and its single crystals were successfully grown. A series of the slow-cooling floating zone experiments revealed that Sr3Zr2O7 melts incongruently into SrZrO3 phase and a liquid and that the compositional range where Sr3Zr2O7 and a liquid coexist is located around 70 mol% SrO composition. Based on the results, we attempted to grow Sr3Zr2O7 single crystals by the traveling solvent floating zone method using SrO-excess solvent and feed. Consequently, many small single crystals of Sr3Zr2O7 phase with several millimeters in size were discovered in the as-grown boules covered with SrO phase. The phase transition behavior of the grown crystals was investigated by differential thermal analysis with polarizing optical microscopy as well as by optical second harmonic generation measurements. We directly observed a reconstruction of orthorhombic twin domains in Sr3Zr2O7 single crystals accompanied by the first-order ferroelectric transition at about 410 °C.

Normal coordinate analysis to study the optical phonons in B-site cation disordered Ruddlesden-Popper Sr3B2O7 (B = V, Cr, Fe, Co) crystals

The Raman and infrared (IR) phonons for the Ruddlesden-Popper Srn+1BnO3n+1 (B = V, Cr, Fe, Co) bilayered tetragonal compounds with n = 2 of symmetry D174h and phase I4/mmm (Z = 2) have been analyzed with Wilson's GF-Matrix Method. Theoretical assignments for the optical wavenumbers have been reported first time for the bilayered tetragonal Sr3V2O7, Sr3Cr2O7, and Sr3Co2O7 compounds by using ten short-range force constants. The appropriate optical vibrational modes have been assigned to the bilayered tetragonal Sr3Fe2O7 compound. The theoretically calculated Raman modes found in the literature are not satisfactorily matched with the experimentally observed frequencies for the bilayered tetragonal Sr3Fe2O7 compound. Using the available data of the isostructural compounds Sr3Ti2O7 and Sr3Mn2O7, we have tried to calculate and report better results for the Raman vibrational modes of the Sr3Fe2O7 compound. Also, we have compared all these three compounds together in terms of frequencies and force constants. The impact of cation-B (B = V, Cr, Fe, Co) exchange on the lattice dynamics of the tetragonal bilayered Sr3B2O7 (B = V, Cr, Fe, Co) isostructural compounds has been analyzed by comparison of the Zone centre vibrational modes, force constants, and bond lengths. For understanding the structure more clearly an attempt is also made to analyze the effect of B-cations (B = V, Cr, Fe, Co) on the affected apical bonds. For each normal mode of the bilayered tetragonal Sr3B2O7 (B = V, Cr, Fe, Co) Ruddlesden-Popper phase, the potential energy distribution (PED) has been analyzed for the significant impact of short-range force constants on different vibrational modes.

Photocatalytic Activity and Stability of Organically Modified Layered Perovskite-like Titanates HLnTiO4 (Ln = La, Nd) in the Reaction of Hydrogen Evolution from Aqueous Methanol

Two series of hybrid inorganic–organic materials, prepared via interlayer organic modification of protonated Ruddlesden–Popper phases HLnTiO4 (Ln = La, Nd) with n-alkylamines and n-alkoxy groups of various lengths, have been systematically studied with respect to photocatalytic hydrogen evolution from aqueous methanol under near-ultraviolet irradiation for the first time. Photocatalytic measurements were organized in such a way as to control a wide range of parameters, including the hydrogen generation rate, quantum efficiency of the reaction, potential dark activity of the sample, its actual volume concentration in the suspension, pH of the medium and stability of the photocatalytic material under the operating conditions. The insertion of the organic modifiers into the interlayer space of the titanates allowed obtaining new, more efficient photocatalytic materials, being up to 68 and 29 times superior in the activity in comparison with the initial unmodified compounds HLnTiO4 and a reference photocatalyst TiO2 P25 Degussa, respectively. The hydrogen evolution rate over the samples correlates with the extent of their interlayer hydration, as in the case of the inorganic–organic derivatives of other layered perovskites reported earlier. However, the HLnTiO4-based samples demonstrate increased stability with regard to the photodegradation of the interlayer organic components as compared with related H2Ln2Ti3O10-based hybrid materials.

Electron-doping Ruddlesden-Popper nickelate

The discovery of cuprate and iron-based superconductors in the last three decades has stimulated a great enthusiasm in researching high T C superconductors. For cuprate, a lot of superconducting compounds were discovered and the superconducting behavior can be tuned by changing the number of the layer. Currently, a cuprate-like superconductor, i.e., nickelate, is reported, which opens a new era in the field of superconductivity. However, the superconducting behavior is only limited in quite a few nickelate compounds. Here, based on first-principles calculations, we investigate the electronic band structure of Ruddlesden Popper (RP) phase and reduced RP (rRP) phase nickelates, and the electron doping influences on these phases. Our results further indicate that the most effective electron-doping selection for these RP/rRP phases is the fluorine replacing the oxygen sites (FO) of LaO or layer to control the electron state. This doping not only introduces electrons to system but also keeps the effective single band. Our theoretical predictions would contribute to the discovering of more possible nickelate superconductors.

Construction of a 3D/2D heterojunction based on a fluorinated cyclohexylamine 2D Ruddlesden–Popper perovskite for highly efficient and stable perovskite solar cells

Nonradiative recombination at perovskite/charge transport layer interfaces is caused by surface defects and instability, and it is known to limit the long-term development of perovskite solar cells (PSCs). To overcome this issue, the three-dimensional/two-dimensional (3D/2D) perovskite heterojunction has emerged as a possible solution to improve the stabilities and efficiency of PSCs. Herein, we employ a simple one-step method to prepare n-i-p-structured PSCs using a 3D/2D perovskite heterojunction as the absorption layer. For this purpose, the large and non-centrosymmetric 4,4-difluorocyclohexylammonium (DFCHA+) cation, which has been confirmed to be a valid organic spacer in 2D Ruddlesden–Popper (RP) phase perovskites, is employed as an organic ligand for post-treatment of the surfaces of MAPbI3 films. The presence of an ultrathin 2D RP phase perovskite was confirmed on the surface, and the 3D/2D perovskite heterojunction was successfully constructed. Benefitting from surface post-treatment, the density of the surface trap states was reduced with effective passivation. In addition, nonradiative recombination was suppressed, and the interface bands were aligned. As a result, the optimal device achieved a power conversion efficiency of 21.93% with a remarkable open-circuit voltage (VOC) of 1.14 V, a current density (JSC) of 23.71 mA cm−2, and a fill factor of 0.82. Furthermore, owing to the hydrophobicity of the DFCHA+ cation, the unencapsulated device was able to maintain an initial efficiency of 82.3% after storage for 500 h at a relative humidity of ∼45%. We believe that this post-treatment strategy has wide application potential in the field of photovoltaic devices.

Passivating Perovskites in Air Via an Alternating Cation Interlayer Phase Formed by Benzylamine Vapor Fumigation

Abstract2D perovskites are widely employed to improve efficiency and stability of perovskite solar cells (PSCs), but the processes are rarely accomplished in air due to the difficulty of controlling the formation processes. An ultra‐thin 2D capping layer with an alternating cation interlayer (ACI) structure is in situ formed by fumigating 3D perovskites with benzylamine vapor. The whole process is finished in air within 10 s regardless of the humidity, after which both defects and tensile strain are reduced and the interfacial energy band gets benignly aligned to a type‐I heterojunction, avoiding direct charge recombination at the interface. Theoretical analysis reveals that the ACI phase is thermodynamically more stable than an analogous Ruddlesden–Popper phase. The strategy can passivate various perovskites, including methylammonium (or multi‐cation) lead (or lead/tin mixed) halide perovskites, prepared via either vapor or solution approaches, increasing the absolute power conversion efficiency by up to 2.5%. It can uniformly passivate PSCs without area limitation, and provide a repeatable methodology for passivating perovskites.

Fabry–Perot Oscillation and Resonance Energy Transfer: Mechanism for Ultralow-Threshold Optically and Electrically Driven Random Laser in Quasi-2D Ruddlesden–Popper Perovskites

The recently emerged metal-halide hybrid perovskite (MHP) possesses superb optoelectronic features, which have obtained great attention in solid-state lighting, photodetection, and photovoltaic applications. Because of its excellent external quantum efficiency, MHP has promising potential for the manifestation of ultralow threshold optically pumped laser. However, the demonstration of an electrically driven laser remains a challenge because of the vulnerable degradation of perovskite, limited exciton binding energy (Eb), intensity quenching, and efficiency drop by nonradiative recombinations. In this work, based on the paradigm of integration of Fabry-Perot (F-P) oscillation and resonance energy transfer, we observed an ultralow-threshold (∼250 μWcm-2) optically pumped random laser from moisture-insensitive mixed dimensional quasi-2D Ruddlesden-Popper phase perovskite microplates. Particularly, we demonstrated an electrically driven multimode laser with a threshold of ∼60 mAcm-2 from quasi-2D RPP by judicious combination of a perovskite/hole transport layer (HTL) and an electron transport layer (ETL) having suitable band alignment and thickness. Additionally, we showed the tunability of lasing modes and color by driving an external electric potential. Performing finite difference time domain (FDTD) simulations, we confirmed the presence of F-P feedback resonance, the light trapping effect at perovskite/ETL, and resonance energy transfer contributing to laser action. Our discovery of an electrically driven laser from MHP opens a useful avenue for developing future optoelectronics.

Spray-Flame Synthesis of LaFexCo1-xO3 (x = 0.2, 0.3) Perovskite Nanoparticles for Oxygen Evolution Reaction in Water Splitting: Effect of Precursor Chemistry (Acetates and Nitrates).

The product properties of mixed oxide nanoparticles generated via spray-flame synthesis depend on an intricate interplay of solvent and precursor chemistries in the processed solution. The effect of two different sets of metal precursors, acetates and nitrates, dissolved in a mixture of ethanol (35 Vol.%) and 2-ethylhexanoic acid (2-EHA, 65 Vol.%) was investigated for the synthesis of LaFexCo1-xO3 (x = 0.2, 0.3) perovskites. Regardless of the set of precursors, similar particle-size distributions (dp = 8-11 nm) were obtained and a few particles with sizes above 20 nm were identified with transmission electron microscopy (TEM) measurements. Using acetates as precursors, inhomogeneous La, Fe, and Co elemental distributions were obtained for all particle sizes according to energy dispersive X-ray (EDX) mappings, connected to the formation of multiple secondary phases such as oxygen-deficient La3(FexCo1-x)3O8 brownmillerite or La4(FexCo1-x)3O10 Ruddlesden-Popper (RP) structures besides the main trigonal perovskite phase. For samples synthesized from nitrates, inhomogeneous elemental distributions were observed for large particles only where La and Fe enrichment occurred in combination with the formation of a secondary La2(FexCo1-x)O4 RP phase. Such variations can be attributed to reactions in the solution prior to injection in the flame as well as precursor-dependent variations in in-flame reactions. Therefore, the precursor solutions were analyzed by temperature-dependent attenuated total reflection Fourier-transform infrared (ATR-FTIR) measurements. The acetate-based precursor solutions indicated the partial conversion of, mainly La and Fe, acetates to metal 2-ethylhexanoates. In the nitrate-based solutions, esterification of ethanol and 2-EHA played the most important role. The synthesized nanoparticle samples were characterized by BET (Brunauer, Emmett, Teller), FTIR, Mössbauer, and X-ray photoelectron spectroscopy (XPS). All samples were tested as oxygen evolution reaction (OER) catalysts, and similar electrocatalytic activities were recorded when evaluating the potential required to reach 10 mA/cm2 current density (∼1.61 V vs reversible hydrogen electrode (RHE)).

Permittivity boosting by induced strain from local doping in titanates from first principles

We examine the effect of isovalent substitutions and co-doping on the ionic dielectric constant of paraelectric titanates (perovskite, Ruddlesden-Popper phases, and rutile) using density functional perturbation theory. Substitutions increase the ionic dielectric constant of the prototype structures, and new dynamically stable structures with εion ~ 102–104 are reported and analyzed. The boosting of ionic permittivity is attributed to local defect-induced strain, and maximum Ti–O bond length is proposed as a descriptor. The Ti–O phonon mode that is responsible for the large dielectric constant can be tuned by a local strain and symmetry lowering from substitutions. Our findings help explain the recently observed colossal permittivity in co-doped rutile, attributing its intrinsic permittivity boosting solely to the lattice polarization mechanism, without the need to invoke other mechanisms. Finally, we identify new perovskite- and rutile-based systems that can potentially display colossal permittivity.

High‐Temperature Equilibrium of 3D and 2D Chalcogenide Perovskites

Chalcogenide perovskites have been recently proposed as novel absorber materials for photovoltaic applications. BaZrS3, the most investigated compound of this family, shows a high absorption coefficient, a bandgap of around 1.8 eV, and excellent stability. In addition to the 3D perovskite BaZrS3, the Ba–Zr–S compositional space contains various 2D Ruddlesden–Popper phases Ban + 1ZrnS3n + 1 (with n = 1, 2, 3) which have recently been reported. Herein, it is shown that at high temperature the Gibbs free energies of 3D and 2D perovskites are very close, suggesting that 2D phases can be easily formed at high temperatures. The product of the BaS and ZrS2 solid‐state reaction, in different stoichiometric conditions, presents a mixture of BaZrS3 and Ba4Zr3S10. To carefully resolve the composition, X‐ray diffraction, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy analysis are complemented with Raman spectroscopy. For this purpose, the phonon dispersions, and the consequent Raman spectra, are calculated for the 3D and 2D chalcogenide perovskites, as well as for the binary precursors. This thorough characterization demonstrates the thermodynamic limitations and experimental difficulties in forming phase‐pure chalcogenide perovskites through solid‐state synthesis and the importance of using multiple techniques to soundly resolve the composition of these materials.

Vapor-Deposited n = 2 Ruddlesden–Popper Interface Layers Aid Charge Carrier Extraction in Perovskite Solar Cells

Interfacial passivation with bulky organic cations such as phenetylammonium iodide has enabled high performance for metal halide perovskite optoelectronic devices. However, the homogeneity of these interfaces and their formation dynamics are poorly understood. We study how Ruddlesden–Popper 2D phases form at a 3D perovskite interface when the 2D precursors are introduced via solution or via vapor. When using vapor deposition, we observe uniform coverage of the capping layer and the formation of a predominantly n = 2 Ruddlesden–Popper phase. In contrast, when using solution deposition, we observe the presence of a mixture of n = 2 and n = 1 in the film and the formation of aggregates of the organic cations. As a result of the better phase purity and uniformity, vapor deposition enables higher median solar cell performance with narrower distribution compared to solution-treated films. This study provides fundamental information that the perovskite community can use to better design capping layers to achieve higher charge extraction efficiencies.

Band Structure and Exciton Dynamics in Quasi‐2D Dodecylammonium Halide Perovskites

AbstractFemtosecond transient absorption spectroscopy (FTAS) is an important tool to investigate the physics of halide perovskites having different dimensionality, morphology, and architectures, giving insights into the electronic and excitonic optical transitions. Here, FTAS on monolayer (n = 1) and multilayer (n = 2, 3) quasi‐2D perovskites in the Ruddlesden–Popper phase: DA2MAn‐1PbnI3n+1 (DAMAPI) is presented, with the dodecylammonium (DA = CH3‐(CH2)11‐NH3+) as the spacer and methylammonium (MA = CH3NH3+) as the organic cation for samples with n &gt; 1. The measurements, performed at 77 K and room temperature using several pump energies and excitation densities, allow the observation of different absorption bleaching energies. Those energies are compared with the results of first‐principles theoretical simulations based on density functional theory, the GW method, and the Bethe–Salpeter equation and assigned to transitions involving excitons with principal quantum numbers 1s and 2s. The temporal analysis of the absorption bleaching indicates the exciton–exciton annihilation as the main relaxation mechanism in the first picoseconds after excitation, while exciton radiative recombination is observed at longer time delays (&gt;100 ps). Therefore, FTAS allows the study of the carrier dynamics and, given its high sensitivity to carrier density changes, the observation of spectral features not observable with steady‐state measurements.

Regulating Radial Morphology in Hot-Casting Two-Dimensional Ruddlesden–Popper Perovskite Film Growth for High-Efficient Photovoltaics

Two-dimensional (2D) perovskites have attracted significant attention in recent years due to their promising light harvesting and emissive properties. However, the realization of 2D perovskite crystallization with sufficient coverage and reliable reproducibility remains difficult. In this study, controlling the solvent volatilization to achieve high-quality crystallization with full coverage and lateral homogeneity of 2D Ruddlesden–Popper phase perovskite was effectively achieved. It is found that variations in the solvent evaporation rate give rise to lateral film coverage gradients with the degree of grain fusion during the process of hot-casting. As a result, the obtained photovoltaic efficiency varies due to the growth inhomogeneity across hot-casting thin films from center to edge. By adjusting the temperature of the casting perovskite precursor, film inhomogeneity and device performance variation can be alleviated. Regulating radial morphology across hot-casting thin films will enable coating techniques amenable to the solution process for robust reproducibility.

Bandgap Tunable Oxynitride LaNb2 O7-x Nx Nanosheets.

Bandgap tunable lanthanum niobium oxynitride [LaNb2 O7-x Nx ](1+x)- nanosheet is prepared by the delamination of a Ruddlesden-Popper phase perovskite oxynitride via ion-exchange and two-step intercalation processes. The lanthanum niobium oxynitride nanosheets have a homogeneous thickness of 1.6nm and exhibit a variety of chromatic colors depending on the nitridation temperature of the parent-layered oxynitride. The bandgap energy of the nanosheets is determined by ultraviolet photoemission spectroscopy, Mott-Schottky, and photoelectrochemical measurements and is found to be tunable in the range of 2.03-2.63eV. Furthermore, the oxide/oxynitride superlattice structures are fabricated by face-to-face stacking of 2D crystals using oxynitride [LaNb2 O7-x Nx ](1+x)- and oxide [Ca2 Nb3 O10 ]- nanosheets as building blocks. Moreover, the superlattices-like restacked oxynitride/oxide nanosheets hybrid exhibits unique proton conductivity and dielectric properties strongly influenced by the oxynitride nanosheets and enhanced photocatalytic activity under visible light irradiation.