Ruddlesden-Popper Faults Research Articles

Simulation of diffraction patterns for Ruddlesden–Popper (RP) tetragonal structures with RP faults

A theoretical analysis of diffraction patterns was performed for two representatives of layered perovskite-type tetragonal phases of the Ruddlesden–Popper series (RP) with the general formula A n+1 B n O3n+1 (n = 1, 2), which contain RP faults (layer alternation defects) in a wide range of concentrations. The results of theoretical calculations can be used in the future for correct interpretation of X-ray powder diffraction experimental data and for quantitative estimation of the deviation from stoichiometry and structural perfection of this type of compound.

Formation of Ruddlesden-Popper Faults in Complex Perovskite Oxides

Formation of Ruddlesden-Popper Faults in Complex Perovskite Oxides

Revealing direct atomic structure and electrostatic maps of the Ruddlesden-Popper faults in LaNiO3 perovskite

Ruddlesden-Popper (RP) faults in perovskites as one type of the anti-phase boundaries provide a versatile platform to manipulate the magnetic, conducting, and magnetoresistance properties in the complex oxides. Local fine structure at the boundaries containing light atoms is a key factor to understand the underlying structure-function relationship due to their interfaces mediated effects. In this work, the atomic structure, chemical distribution and electronic structure of typical RP faults in perovskite LaNiO3 and its epitaxial nanocomposite films on a SrTiO3 substrate were systematically investigated combining high-resolution scanning transmission electron microscopy (STEM) and density functional theory (DFT) calculations. Integrated differential phase contrast (iDPC) STEM imaging results demonstrate a NiO2-x-(LaO-LaO)-NiO2-x atomic configuration with content fluctuations of oxygen at the RP faults. Atomic electronic energy loss spectroscopy results and DFT calculations illustrate that Ni cations have mixed valence of Ni2+, Ni3+ at the RP faults accompanying with oxygen environment fluctuations affected by the non-stoichiometric bonding. This study offers a comprehensive route to explore intriguing chemical structures and physical properties in the homointerface structure at the atomic level.

Tailoring of Photoluminescence Properties in All‐Vacuum Deposited Perovskite via Ruddlesden–Popper Faults

AbstractRuddlesden–Popper (RP) faults are well known in oxide perovskites, and are also observed in promising metal halide perovskites. However, the effect of RP faults on optical properties of perovskite has not been systematically investigated. In this study, it is found that RP faults are common planar faults in all‐vacuum deposited CsPbBr3‐based perovskite polycrystal thin films, and the density of RP planar faults can be greatly increased by non‐stoichiometric composition (Cs‐rich) as well as reduced dimensionality (quasi‐2D) strategies. The photoluminescence (PL) measurement reveals monotonically increasing peak intensities with higher densities of RP planar faults from Cs‐rich, quasi‐2D to Cs‐rich & quasi‐2D samples. The corresponding atomic‐scale differential phase contrast maps indicate strongly confined charges within the RP planar fault network, which explains well the relationship between PL enhancement and the density of RP planar faults, and offers an alternative pathway for tailoring the optoelectronic properties of perovskite.

High-mobility electron gas in Sr2TiO4/SrTiO3 heterostructure engineered by vertical Ruddlesden–Popper faults

High-mobility electron gases in SrTiO3-based heterostructures have been mainly synthesized on single TiO2 terminated SrTiO3 substrates. Here, we show a high-mobility electron gas observed in a Sr2TiO4/SrTiO3 heterostructure based on an untreated SrTiO3 substrate with mixed termination, showing the mobility value up to 28 000 cm2 V−1 s−1 at 2 K. SrO–SrO vertical Ruddlesden–Popper faults in the Sr2TiO4 film provide escape channels for oxygen atoms under high temperatures, enabling the as-grown tuning of oxygen vacancies in the SrTiO3 layer during film deposition and reversible after-growth modulation in a thermal annealing process.

Atomic-Scale Mapping and Quantification of Local Ruddlesden-Popper Phase Variations.

The Ruddlesden-Popper (An+1BnO3n+1) compounds are highly tunable materials whose functional properties can be dramatically impacted by their structural phase n. The negligible differences in formation energies for different n can produce local structural variations arising from small stoichiometric deviations. Here, we present a Python analysis platform to detect, measure, and quantify the presence of different n-phases based on atomic-resolution scanning transmission electron microscopy (STEM) images. We employ image phase analysis to identify horizontal Ruddlesden-Popper faults within the lattice images and quantify the local structure. Our semiautomated technique considers effects of finite projection thickness, limited fields of view, and lateral sampling rates. This method retains real-space distribution of layer variations allowing for spatial mapping of local n-phases to enable quantification of intergrowth occurrence and qualitative description of their distribution suitable for a wide range of layered materials.

Blue Perovskite Nanocrystal Light-Emitting Diodes: Overcoming RuddlesdenPopper Fault-Induced Nonradiative Recombination via Post-Halide Exchange.

Metal halide perovskites (MHPs) have gained traction as emitters owing to their excellent optical properties, such as facile bandgap tuning, defect tolerance, and high color purity. Nevertheless, blue-emitting MHP light-emitting diodes (LEDs) show only marginal progress in device efficiency compared with green and red LEDs. Herein, the origin of the drop in efficiency of blue-emitting perovskite nanocrystals (PNCs) by mixing halides and the genesis of Ruddlesden-Popper faults (RPFs) in CsPbBrX Cl3-X nanocrystals is investigated. Using scanning transmission electron microscopy and density functional theory calculations, the authors have found that RPFs induce possible nonradiative recombination pathways owing to the high chloride vacancy concentration nearby. The authors further confirm that the blue-emitting PNCs do not show RPFs post-halide exchange in the CsPbBr3 nanocrystals. By introducing the post-halide exchange treatment, high-efficiency pure blue-emitting (464nm) PNC-based LEDs with an external quantum efficiency of 2.1% and excellent spectral stability with a full-width at half-maximum of 14nm are obtained.

Weak magnetic field-dependent photoluminescence properties of lead bromide perovskites

The strong spin–orbit coupling (SOC) in lead halide perovskites, when inversion symmetry is lifted, has provided opportunities for investigating the Rashba effect in these systems. Moreover, the strong orbital moment, which, in turn, impacts the spin-pair in singlet and triplet electronic states, plays a significant role in enhancing the optoelectronic properties in the presence of external magnetic fields in lead halide perovskites. Here, we investigate the effect of weak magnetic fields (<1 T) on the photoluminescence (PL) properties of CsPbBr3 nanocrystals with and without Ruddlesden–Popper (RP) faults and single crystals of CH3NH3PbBr3. Along with an enhancement in the PL intensity as a function of an external magnetic field, which is observed in both lead bromide perovskites, the PL emission red-shifts in CsPbBr3 nanocrystals. Density-functional theory calculations of the electronic band-edge in CsPbBr3 show almost no change in the energy gap as a function of the external magnetic field. The experimental results, thus, suggest the role of mixing of the triplet and singlet excitonic states under weak magnetic fields. This is further deduced from an enhancement in PL lifetimes as a function of the field in CsPbBr3. In CH3NH3PbBr3, an increase in PL intensity is observed under weak magnetic fields; however, no changes in the peak energy or PL lifetimes are observed. The internal magnetic fields due to SOC are characterized for all three samples and found to be the highest for CsPbBr3 nanocrystals with RP faults.

Unravelling Structure and Formation Mechanisms of Ruddlesden-Popper-Phase-like Nanodomains in Inorganic Lead Halide Perovskites.

Ultrastable CsPbBr3 nanoplates against electron beam irradiations are fabricated and nanodomains with anomalous high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) contrasts are observed within CsPbBr3 nanoplates. Atomic resolution energy dispersive X-ray spectroscopy (EDS) mapping, which requires even higher beam currents and may cause significant damages on electron beam sensitive materials, are obtained without any detectable damages or decomposition. Combining HAADF-STEM images, atomic resolution EDS mapping, and image simulations has revealed detailed structure and chemistry of the nanodomains to be induced by Ruddlesden-Popper faults (RP faults) rather than any chemical intermixing or formation of new phases. A formation mechanism is also proposed on the basis of the atomic structure of the nanodomains. This result promotes an atomic-level understanding of inorganic lead halide perovskites and may help to reveal their structure-property relationship.

Ruddlesden–Popper Faults in NdNiO3 Thin Films

The NdNiO3 (NNO) system has attracted a considerable amount of attention owing to the discovery of superconductivity in Nd0.8Sr0.2NiO2. In rare-earth nickelates, Ruddlesden–Popper (RP) faults play a significant role in functional properties, motivating our exploration of its microstructural characteristics and the electronic structure. Here, we employed aberration-corrected scanning transmission electron microscopy and spectroscopy to study a NdNiO3 film grown by layer-by-layer molecular beam epitaxy (MBE). We found RP faults with multiple configurations in high-angle annular dark-field images. Elemental intermixing occurs at the SrTiO3–NdNiO3 interface and in the RP fault regions. Quantitative analysis of the variation in lattice constants indicates that large strains exist around the substrate–film interface. We demonstrate that the Ni valence change around RP faults is related to a strain and structure variation. This work provides insights into the microstructure and electronic-structure modifications around RP faults in nickelates.

Inorganic Ruddlesden-Popper Faults in Cesium Lead Bromide Perovskite Nanocrystals for Enhanced Optoelectronic Performance.

While the layered hybrid Ruddlesden-Popper (RP) halide perovskites have already established themselves as the frontrunners among the candidates in optoelectronics, their all-inorganic counterparts remain least explored in the RP-type perovskite family. Herein, we study and compare the optoelectronic properties of all-inorganic CsPbBr3 perovskite nanocrystals (PNCs) with and without RP planar faults. We find that the RP-CsPbBr3 PNCs possess both higher exciton binding energy and longer exciton lifetimes. The former is ascribed to a quantum confinement effect in the PNCs induced by the RP faults. The latter is attributed to a spatial electron-hole separation across the RP faults. A striking difference is found in the up-conversion photoluminescence response in the two types of CsPbBr3 PNCs. For the first time, all-inorganic RP-CsPbBr3 PNCs are tested in light-emitting devices and shown to significantly outperform the non-RP CsPbBr3 PNCs.

Generation of Ruddlesden-Popper faults in Sr doped NdNiO3

Generation of Ruddlesden-Popper faults in Sr doped NdNiO₃

Barriers to carriers: faults and recombination in non-stoichiometric perovskite scintillators

Tuning the efficiency and speed of charge carrier recombination in inorganic scintillators can potentially improve their performance in diverse applications. Recent work suggests that this maybe be achieved via a two-phase scintillator AB that naturally phase separates into A-rich and B-rich domains. In addition, a favorable electronic structure and band-edge alignment such that the charge carriers are confined or are thermodynamically driven to preferentially accumulate in one of the two domains, might lead to an improved radiative recombination rate. Here, we use density functional theory computations and ab initio molecular dynamics (AIMD), including non-adiabatic molecular dynamics (NAMD) simulations, to examine an alternative phase structure and its potential impact on recombination. Using a model perovskite SrTiO_3 system with one-, two- and three-dimensional Ruddlesden–Popper (RP) phases, we demonstrate that RP faults induce band structure changes in the material that can act as barriers to carrier transport. Our AIMD/NAMD simulations indicate competing effects of a lower mean free path (potentially enhancing the desired radiative recombination and overall scintillating efficiency) and faster non-radiative recombination (undesired) due to enhanced electron–phonon coupling in the faulted system. Full exploitation of such a rational design approach would require tuning of the effective scintillation efficiency by varying the perovskite chemistry using appropriate arrangements of RP faults in the bulk material. Finally, other effects, such as the tendency of point defects to segregate at the interface, that might affect the overall performance, are briefly discussed. We expect the basic results found here to apply to other nanostructured scintillators.Graphical

Revealing a high-density three-dimensional Ruddlesden–Popper-type fault network in an SmNiO3 thin film

An epitaxial SmNiO3 thin-film grown on an LaAlO3 (001) substrate using pulsed laser deposition is investigated with spherical-aberration corrected scanning transmission electron microscopy techniques, including high-angle annular dark field, X-ray energy dispersive, and electron energy-loss spectroscopy. High-density Ruddlesden–Popper (RP)-type faults, which generate two types of image contrast due to overlaps along the electron beam direction, are identified with the translational vector of 1/2a⟨111⟩c, corresponding to 1/2a⟨101⟩c displacement of Sm atoms when observed along the [010]c zone axis. These defects originate from Sm-rich non-stoichiometry within the SmNiO3, and their directions depend on the local stress states. Lattice distortion induced by the RP faults reduces the metal-to-insulator transition temperature to around 340 K. The effects of high-density RP faults on the lattice strain, domain size, and strong electronic-lattice correlations indicate that RP faults can provide extra freedom to tailor the physical properties of SmNiO3 thin films for potential electronic device applications. High-density Ruddlesden–Popper-type faults are revealed in an epitaxial SmNiO3 thin film grown on LaAlO3 (001) by pulsed laser deposition, originating from Sm-rich non-stoichiometry, and their directions depend on the local stress states. Lattice distortion induced by the RP faults reduces the metal-to-insulator transition temperature to around 340 K. RP faults provide extra freedom to tailor intriguing properties of SmNiO3 for potential electronic device applications.

Formation mechanism of Ruddlesden-Popper faults in compressive-strained ABO3 perovskite superlattices.

Ruddlesden-Popper (RP) faults have emerged as a promising candidate for defect engineering in epitaxial ABO3 perovskites. Functionalities could be fine-tuned by incorporating RP faults into ABO3 thin films and superlattices. However, due to the lattice expansion at AO-AO interfaces, it is generally believed that RP faults are only energetically favorable under tensile strain. Contrary to this common cognition, here we present that compressive strain must be regarded as an alternative driving force for creating RP faults. Unlike the conventional perovskite-to-rock-salt transition, the RP faults originated from Shockley partial dislocations bounded by stacking faults on the basal plane. The edge-type partials gave rise to strain relaxation, facilitating the formation of RP faults under compressive strain. We envisage that our results will give new insights into the rational design and defect engineering in epitaxial-strained ABO3 perovskites.

Observation of fault-free coherent layer during Ruddlesden–Popper faults generation in LaNiO3 thin films

Two-dimensional lattice defects, including surface and grain boundaries, in various perovskite oxides have garnered considerable attention, as the overall physical properties of the oxides can significantly vary depending on the atomic and electronic structure of the defects. In particular, because Ruddlesden–Popper (RP) planar faults have a unique lattice structure with [AO] monolayers being inserted in an ABO3 perovskite framework, they have attracted considerable attention, resulting in various relevant studies being conducted. This study focuses on the effect of lattice strain on formation of RP faults and on critical thickness in (001) epitaxial LaNiO3 thin-film fabrication through a sol–gel process. Atomic-scale direct observations identifies that a fault-free coherent buffer layer forms during the RP fault generation and its thickness varies depending on the strain exerted from the substrate. When DyScO3, the lattice mismatch of which is the largest, is used as a substrate, the critical thickness of the fault-free buffer layer remarkably reduces to a few unit cells. This work highlights the significance of direct observation to understand the defect formation in perovskite oxides.

Effect of Lattice Strain on the Formation of Ruddlesden-Popper Faults in Heteroepitaxial LaNiO3 for Oxygen Evolution Electrocatalysis.

A great deal of research has recently been focused on Ruddlesden-Popper (RP) two-dimensional planar faults consisting of intervened [AO] monolayers in an ABO3 perovskite framework due to the structurally peculiar shear configuration. In this work, we scrutinize the effect of elastic strain on the generation behavior of RP faults, which are electrocatalytically very active sites for the oxygen evolution reaction (OER), in (001) epitaxial LaNiO3 thin films through by using two distinct single-crystal substrates with different cubic lattice parameters. Atomic-scale direct observations reveal that RP faults can be more favorably created when tensile misfit strain is exerted. Furthermore, we demonstrate that the controlled growth of thin films show notably enhanced OER activity by the RP faults. The findings in this study highlight the impact of symmetry-breaking defect formation for better oxygen electrocatalysis in perovskite oxides.

Pressure-Induced Phase Changes in Cesium Lead Bromide Perovskite Nanocrystals with and without Ruddlesden–Popper Faults

Lead halide perovskites have a rich landscape of structural and optical properties, which can be explored and possibly controlled by applying high pressure. Despite several reports on high-pressure...

Catalytic Enhancement of CO Oxidation on LaFeO3 Regulated by Ruddlesden-Popper Stacking Faults.

The influence of planar defects, in the form of stacking faults, within perovskite oxides on catalytic activity has received little attention because controlling stacking-fault densities presents a major synthetic challenge. Furthermore, stacking faults in ceramics are not thought to appreciably impact surface chemistry, which partly explains why their direct effect on catalysis is generally ignored. Here, we show that Ruddlesden-Popper (RP) stacking faults in otherwise stoichiometric LaFeO3 can be broadly controlled by modulating the ceramic synthesis route. Electronic structure calculations along with electron microscopy and spectroscopy show that energetically favorable RP faults occur both near the surface and in bunches and enhance CO oxidation kinetics. Density functional theory (DFT) + U shows that subsurface RP faults strengthen the adsorption and co-adsorption of CO, O, and O2, which could lower the apparent activation energy of CO oxidation on faulted catalysts compared to that on their pristine counterparts. Our work suggests that planar defects should be considered a new and useful feature in hierarchal nanoscale design of future catalysts.

Atomic Structure and Electrical Activity of Grain Boundaries and Ruddlesden-Popper Faults in Cesium Lead Bromide Perovskite.

To evaluate the role of planar defects in lead-halide perovskites-cheap, versatile semiconducting materials-it is critical to examine their structure, including defects, at the atomic scale and develop a detailed understanding of their impact on electronic properties. In this study, postsynthesis nanocrystal fusion, aberration-corrected scanning transmission electron microscopy, and first-principles calculations are combined to study the nature of different planar defects formed in CsPbBr3 nanocrystals. Two types of prevalent planar defects from atomic resolution imaging are observed: previously unreported Br-rich [001](210)∑5 grain boundaries (GBs) and Ruddlesden-Popper (RP) planar faults. The first-principles calculations reveal that neither of these planar faults induce deep defect levels, but their Br-deficient counterparts do. It is found that the ∑5 GB repels electrons and attracts holes, similar to an n-p-n junction, and the RP planar defects repel both electrons and holes, similar to a semiconductor-insulator-semiconductor junction. Finally, the potential applications of these findings and their implications to understand the planar defects in organic-inorganic lead-halide perovskites that have led to solar cells with extremely high photoconversion efficiencies are discussed.