A-site Cation Ordering Research Articles

Global Optimization of Cation Ordering in Perovskites by Recommendation-Based Basin-Hopping.

Cation ordering in multication perovskites is related to many important material properties and performances, but computational determination of the cation ordering remains a major challenge. Here, we propose a new computational approach by introducing a machine learning recommender system into the basin-hopping framework (RBH) for optimizing cation ordering. Taking the electrocatalyst Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF5582) as a showcase example, we found that the efficiency of RBH in identifying low-energy configurations outperforms the methods of cluster expansion and conventional basin-hopping. The RBH results revealed that the BSCF5582 catalyst tended to have a layered ordering of A-site cations and disordered B-site cations both in bulk and on the surfaces. Further, on the A-site-terminated surface, we found the segregation of large Ba atoms. Similarly, on the A-site- terminated surface of the recently developed Cs0.2Sr0.8Co0.4Fe0.6O3 (CSCF2846) catalyst, layered ordering at the A-site and surface enrichment of large Cs atoms were also found. The layered ordering was robust against thermal effects, as found from molecular dynamics simulations at 800 K. This work provides a new approach for thermodynamic global optimization of chemical ordering in multicomponent materials.

Investigating structural, phonons, optoelectronics, and thermodynamic properties of lead-free double perovskites of A-site cation ordering in LiXTl2Cl6 (X= Sc and Y) compounds for green energy applications

This study explores the structural, phonons, optoelectronic, and thermodynamic properties of LiXTl2Cl6 (X = Sc and Y) compounds. These double perovskite materials are particularly interesting due to their potential for green energy applications. We employ state-of-the-art computational simulation techniques to investigate the structural properties of these compounds, focusing on the cation ordering in the A-site of the perovskite structure. Through density functional theory (DFT) calculations, we determine the equilibrium crystal structure and lattice parameters, shedding light on the stability of these materials. Furthermore, we analyze the phonon spectra to assess the materials' vibrational properties, including the presence of any phonon modes that may impact thermal stability and thermal transport. Optoelectronic properties, such as band gaps and optical absorption spectra, are also explored to evaluate the suitability of these materials for photovoltaic and light-emitting applications. We investigate their electronic structure and consider the potential for efficient charge carrier generation and transport. The thermodynamic properties, such as heat capacity, entropy, and enthalpy, are calculated to provide insight into the compounds' thermal behavior under various environmental conditions, which is crucial for green energy applications, including thermal energy conversion. This comprehensive investigation into the LiXTl2Cl6 (X = Sc and Y) compounds aims to contribute to developing lead-free double perovskite materials with tailored properties for a range of green energy applications, paving the way for more sustainable and environmentally friendly energy solutions.

Anisotropic Thermal Expansion and a Second-Order Charge Order Transition in the Ferrimagnetic Dy2CuZnMn4O12 Perovskite with Triple A-Site Cation Ordering.

Dy2CuZnMn4O12 perovskite, belonging to the A-site columnar-ordered quadruple perovskite family with the general composition of A2A'A″B4O12, was prepared by a high-pressure, high-temperature method at 6 GPa and 1500 K. Its crystal structure was studied by synchrotron powder X-ray diffraction between 100 and 800 K. The ideal cation distribution (without antisite disorder) was found to be realized within the sensitivity of the synchrotron X-ray diffraction method. Between 100 and 400 K, it crystallizes in space group Pmmn (no. 59) and has layered charge ordering of Mn3+ and Mn4+ at the B sites. Above 425 K, it crystallizes in space group P42/nmc (no. 137) with one crystallographic B site and an average Mn3.5+ oxidation state. The charge ordering transition (at TCO = 425 K) appears to be of the second order as no anomalies were found on differential scanning calorimetry curves and temperature dependence of the unit cell volume, and the orthorhombic a and b lattice parameters merge gradually. The compound demonstrates anisotropic thermal expansion with the c lattice parameter decreasing with increasing temperature above 280 K. A ferrimagnetic transition occurs at TC = 116 K with an additional, gradual rise of magnetic susceptibilities below 45 K, probably due to increases of the ordered moments of the Dy sublattices.

Tailoring Ion Ordering in Perovskite Oxide for High-Temperature Oxygen Evolution Reaction.

Perovskites exhibit excellent high-temperature oxygen evolution reaction (OER) activities as the anodes of solid oxide electrolysis cells (SOECs). However, the relationship between ion ordering and OER performances is rarely investigated. Herein, a series of PrBaCo2-x Fex O5+δ perovskites with tailored ion orderings are constructed. Physicochemical characterizations and density functional theory calculations confirm that the oxygen bulk migration and surface transport capacities as well as the OER activities are promoted by the A-site cation ordering, but weakened by the oxygen vacancy ordering. Hence, SOEC with the A-site-ordered and oxygen-vacancy-disordered PrBaCo2 O5+δ anode exhibits the highest performance of 3.40 A cm-2 at 800 °C and 2.0 V. This work sheds light on the critical role of ion orderings in the high-temperature OER performance and paves a new way for screening novel anode materials of SOECs.

Insights into Cation Ordering of Double Perovskite Oxides from Machine Learning and Causal Relations

This work investigates the origins of cation ordering of double perovskites using first-principles theory computations combined with machine learning (ML) and causal relations. We have considered various oxidation states of A, A', B, and B' from the family of transition metal ions to construct a diverse compositional space. A conventional framework employing traditional ML classification algorithms such as Random Forest (RF) coupled with appropriate features including geometry-driven and key structural modes leads to highly accurate prediction (~98%) of A-site cation ordering. We have evaluated the accuracy of ML models by entailing analyses of decision paths, assignments of probabilistic confidence bound, and finally introducing a direct non-Gaussian acyclic structural equation model to investigate causality. Our study suggests that the structural modes are the most important features for classifying layered, columnar and rock-salt ordering. For clear layered ordering, the charge difference between the A and A' is the most important feature which in turn depends on the B, B' charge separation. Based on the outputs from ML models, we have designed functional forms with these features to derive energy differences forming clear layered ordering. The trilinear coupling between tilt, rotation, and A-site antiferroelectric displacement in Landau free-energy expansion becomes the necessary condition behind the formation of A-site cation ordering.

Structural, Magnetic, and Electrical Properties of Doubly Ordered Perovskites NaLnNiWO6 (Ln = La, Pr, Nd, Sm, Eu, Gd, and Tb)

We report the structural, magnetic, and electrical properties of a new family of doubly ordered perovskites NaLnNiWO6 (Ln = La, Pr, Nd, Sm, Eu, Gd, and Tb), synthesized at high-pressure (4.5 GPa) and high-temperature (1000 °C) conditions. These materials crystallize in the monoclinic structure with the polar space group P21 as revealed by neutron diffraction (Ln = La), X-ray diffraction, and second-harmonic-generation (SHG) studies. These compounds exhibit a combined layered ordering of A-site cations and rock-salt ordering of B-site cations with octahedral tilting, which breaks the inversion symmetry and results in a polar structure. The magnetic and heat capacity measurements reveal the antiferromagnetic order of Ni2+ ion moments in the temperature range of 23–30 K, depending on the Ln ion. Analysis of neutron powder diffraction data for the La compound reveals that the Ni2+ spins couple antiferromagnetically along the a- and c-directions and ferromagnetically along the b-axis, consistent with the propagation vector, k = (1/2, 0, 1/2). In contrast to the compounds with smaller lanthanide ions (Ln = Y, Dy, Ho, and Yb), these compounds do not exhibit measurable electric polarization at TN but show a dielectric anomaly.

Hybrid improper ferroelectricity in A-site cation ordered Li2La2Ti3O10 ceramic with triple-layer Ruddlesden–Popper structure

Hybrid improper ferroelectricity has been extensively studied in double-layer Ruddlesden–Popper oxides in recent years. Although the hybrid improper ferroelectricity could be created among triple-layer Ruddlesden–Popper oxides with an ordered A-site cation predicted by the first-principles calculations, no experimental result has been reported yet. In the present work, the room-temperature ferroelectricity has been observed in Li2La2Ti3O10 ceramics with an A-site cation ordered triple-layer Ruddlesden–Popper structure. The polar phase P21ab has been determined by combining the first-principles calculation and the powder diffraction analysis at room temperature. The hybrid improper ferroelectricity was induced by the triple-coupled irreps including the A-site cation ordering. The variable temperature differential scanning calorimetry measurements and dielectric responses indicate no evidence of phase transition over the temperature range of 200–1080 K. The present work sheds light on designing the hybrid improper ferroelectrics in A-site ordered triple-layer Ruddlesden–Popper compounds.

A-Site and B-Site Cation Ordering Induces Polar and Multiferroic Behavior in the Perovskite NaLnNiWO6 (Ln = Y, Dy, Ho, and Yb)

Octahedral distortion in ABO3 perovskite materials is ubiquitous because of the ionic size mismatch between A and B cations, leading to various kinds of crystal symmetry. However, such a distortion always results in centrosymmetric structures except for the covalent bond formation because of the second-order Jahn–Teller (SOJT) effect that occurs with d0 or lone-pair cations. Here, we report that an unusual combination of the layered A-site cation ordering and B-site rock salt ordering in NaYNiWO6 prepared under high-pressure and high-temperature conditions results not only in a polar (P21) structure, as revealed by the neutron diffraction analysis, but exhibits multiferroic properties below the magnetic ordering of Ni2+ ions (TN = 21 K). Analysis of the neutron diffraction data at 20 K reveals an incommensurate sinusoidal spin ordering with the propagation vector, ki = (0.471(2), 0, 0.491(4)), and a commensurate collinear spin structure with kc = (0.5, 0, 0.5) below 18 K. X-ray diffraction data confirm the polar structure in Dy, Ho, and Yb compounds. All four compounds exhibit a switchable change in electric polarization (ΔP) at the magnetic ordering temperatures, demonstrating coupling between ferroelectricity and magnetism.

Highly active hydrogen evolution catalysis on oxygen-deficient double-perovskite oxide PrBaCo2O6−δ

Oxygen-deficient double perovskite oxides PrBaCo2O6−δ exhibit highly active hydrogen evolution reaction catalysis, which is associated with multiple factors: oxygen deficiency, high Co valence, and A-site cation ordering.

Expanding the Doubly Cation Ordered AA′BB′O6 Perovskite Family: Structural Complexity in NaLaInNbO6 and NaLaInTaO6

Two new perovskite compounds, NaLaInNbO6 and NaLaInTaO6, have been synthesized. Both compounds have a rock-salt ordering of the In/Nb or In/Ta cations and a layered ordering of the Na/La. They are unusual among this family of doubly cation ordered perovskites for having a +3/+5 combination of B/B' oxidation states instead of a divalent cation and W6+. Synchrotron powder diffraction and electron diffraction data show both compounds have tetragonal √2ap × √2ap × 2ap unit cells. The octahedral tilt system of these compounds is complicated and seems to vary depending on the length scale considered. Bond valence considerations demonstrate that none of the tilt systems compatible with a tetragonal unit cell produce a stable structure. It is proposed that additional oxygen displacements are occurring on a local scale. The XRD data show that the B-site ordering is nearly complete in both cases, while the A-site cations show a lower degree of order. The tendency of the B'-cation to undergo a second order Jahn-Teller distortion is identified as having an influence over the degree of A-site ordering. Transmission electron microscopy shows fragmentation into nanosized domains with perpendicular orientations of the layered A-site cation ordering. Such structures may be polar over short length scales which could lead to interesting dielectric properties such as relaxor behavior. The prospects for finding new doubly cation ordered perovskites are also discussed.

A group-theoretical approach to enumerating magnetoelectric and multiferroic couplings in perovskites.

A group-theoretical approach is used to enumerate the possible couplings between magnetism and ferroelectric polarization in the parent Pm{\overline 3}m perovskite structure. It is shown that third-order magnetoelectric coupling terms must always involve magnetic ordering at the A and B sites which either transforms both as R-point or both as X-point time-odd irreducible representations (irreps). For fourth-order couplings it is demonstrated that this criterion may be relaxed allowing couplings involving irreps at X-, M- and R-points which collectively conserve crystal momentum, producing a magnetoelectric effect arising from only B-site magnetic order. In this case, exactly two of the three irreps entering the order parameter must be time-odd irreps and either one or all must be odd with respect to inversion symmetry. It is possible to show that the time-even irreps in this triad must transform as one of: X1+, M3,5- or R5+, corresponding to A-site cation order, A-site antipolar displacements or anion rocksalt ordering, respectively. This greatly reduces the search space for type-II multiferroic perovskites. Similar arguments are used to demonstrate how weak ferromagnetism may be engineered and a variety of schemes are proposed for coupling this to ferroelectric polarization. The approach is illustrated with density functional theory calculations on magnetoelectric couplings and, by considering the literature, suggestions are given of which avenues of research are likely to be most promising in the design of novel magnetoelectric materials.

Structural Modification of the Cation-Ordered Ruddlesden-Popper Phase YSr2Mn2O7 by Cation Exchange and Anion Insertion.

Calcium-for-strontium cation substitution of the a-b0c0/b0a-c0-distorted, cation-ordered, n = 2 Ruddlesden-Popper phase, YSr2Mn2O7, leads to separation into two phases, which both retain an a-b0c0/b0a-c0-distorted framework and have the same stoichiometry but exhibit different degrees of Y/Sr/Ca cation order. Increasing the calcium concentration to form YSr0.5Ca1.5Mn2O7 leads to a change in the cooperative tilting on the MnO6 units to a novel a-b-c-/b-a-c- arrangement described in space group P21/n11. Low-temperature, topochemical fluorination of YSr2Mn2O7 yields YSr2Mn2O5.5F3.5. In contrast to many other fluorinated n = 2 Ruddlesden-Popper oxide phases, YSr2Mn2O5.5F3.5 retains the a-b0c0/b0a-c0 lattice distortion and P42/mnm space group symmetry of the parent oxide phase. The resilience of the a-b0c0/b0a-c0-distorted framework of YSr2Mn2O7 to resist symmetry-changing deformations upon both cation substitution and anion insertion/exchange is discussed on the basis the A-site cation order of the lattice and the large change in the ionic radius of manganese upon oxidation from Mn3+ to Mn4+. The structure property relations observed in the Y-Sr-Ca-Mn-O-F system provide insight into assisting in the synthesis of n = 2 Ruddlesden-Popper phases, which adopt cooperative structural distortions that break the inversion symmetry of the extended lattice and therefore act as a route for the preparation of ferroelectric and multiferroic materials.

Local Structure of Disordered Bi0.5K0.5TiO3 Investigated by Pair Distribution Function Analysis and First-Principles Calculations

We investigate A-site cation ordering in the ferroelectric perovskite Bi0.5K0.5TiO3 (BKT) by density functional theory (DFT) calculations and synchrotron X-ray total scattering. Using BKT as a prototypical lead-free ferroelectric perovskite with mixed A-site cations, we use a combination of theory and experiments to assess the energetics and resulting physical properties of cation ordering. Ten different Bi/K configurations in a 2 × 2 × 2 supercell were assessed by real space pair distribution functions (PDFs) and DFT calculations. None of these configurations were identified as particularly favorable from experiment or theory. Ferroelectric polarization calculated by the Berry phase method for all ten configurations yields values of 50–105 μC/cm2. This is significantly larger than previously reported experimental results in the range of 22–49 μC/cm2, indicating that BKT does not possess long-range A-site cation order. Reverse Monte Carlo (RMC) modeling of the total scattering data with a 12 × 12 × 12 sup...

Normal-relaxor ferroelectric modulation of a-site complex perovskite ferroelectric (K1/2Bi1/2)TiO3 by post-annealing

In this work, the A-site complex perovskite K1/2Bi1/2TiO3 (KBT) was first found to demonstrate a normal-relaxor ferroelectric modulation by the annealing temperature. KBT ceramics were synthesized by the solid-state reaction method and subjected to a post-annealing at 800 °C or 1000 °C, respectively. It is found that the post-annealing at 800 °C switches KBT to a relaxor ferroelectric while the post-annealing at 1000 °C makes KBT develop into a normal ferroelectric. Besides, the sample annealed at 800 °C presented an inflection at 155 °C to decrease the Pr due to the enhanced relaxor behavior. Moreover, annealing at 1000 °C could promote the growth of the domains and the local ordering of A-site cations. It is believed that the modulation of KBT between the normal ferroelectric and relaxor was attributed to the domain size and the local ordering of A-site cations.

La2SrCr2O7: Controlling the Tilting Distortions of n = 2 Ruddlesden-Popper Phases through A-Site Cation Order.

Structural characterization by neutron diffraction, supported by magnetic, SHG, and μ(+)SR data, reveals that the n = 2 Ruddlesden-Popper phase La2SrCr2O7 adopts a highly unusual structural configuration in which the cooperative rotations of the CrO6 octahedra are out of phase in all three Cartesian directions (ΦΦΦz/ΦΦΦz; a(-)a(-)c(-)/a(-)a(-)c(-)) as described in space group A2/a. First-principles DFT calculations indicate that this unusual structural arrangement can be attributed to coupling between the La/Sr A-site distribution and the rotations of the CrO6 units, which combine to relieve the local deformations of the chromium-oxygen octahedra. This coupling suggests new chemical "handles" by which the rotational distortions or A-site cation order of Ruddlesden-Popper phases can be directed to optimize physical behavior. Low-temperature neutron diffraction data and μ(+)SR data indicate La2SrCr2O7 adopts a G-type antiferromagnetically ordered state below TN ∼ 260 K.

Enhanced luminescence of a Eu3+-activated double perovskite (Na, Li)LaMgWO6 phosphor based on A site inducing energy transfer

Li+ ion substituted Na1−xLixLa0.95Eu0.05MgWO6 phosphors were successfully synthesized by an improved sol-gel method using citric acid and polyethylene glycol as complexing agents. The structural evolution was systematically investigated by X-ray diffraction with Rietveld structure refinement and Raman spectra. The layered ordering of A-site cations and a second-order Jahn-Teller distortion of B’ cations simultaneously existed in this double perovskite. The decreased symmetry and lattice parameters within the same space group C2/m were observed from the Li+ substituted powders. Upon increasing the Li+ concentration, the absorption intensities of the 4f−4f transitions of Eu3+ monotonically increased. Likewise, the intensity of 5D0-7F2 monotonically increased under the excitations of both near-ultraviolet and blue light, with an enhancement of ten- and six-fold, respectively. The relative intensity ratio of red/orange emissions gradually increased, and the CIE chromaticity coordinates gradually approached those of standard red light. “A site inducing energy transfer” in double perovskite was achieved by selecting a substitution element with a small radius.

Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior.

Thermal Expansion and Second Harmonic Generation Response of the Tungsten Bronze Pb2AgNb5O15.

The incorporation of transition metal element Ag was performed to explore negative thermal expansion (NTE) materials with tetragonal tungsten bronze (TTB) structures. In this study, the structure and thermal expansion behaviors of a polar TTB oxide, Pb2AgNb5O15 (PAN), were systematically investigated by high-resolution synchrotron powder diffraction, high-resolution neutron powder diffraction, transmission electron microscope (TEM), and high-temperature X-ray diffractions. The TEM and Rietveld refinements revealed that the compound PAN displays (√2a(TTB), √2b(TTB), 2c(TTB))-type superstructure. This superstructure within the a-b plane is caused by the ordering of A-site cations, while the doubling of the c axis is mainly induced by a slight tilt distortion of the NbO6 octahedra. The transition metal Ag has larger spontaneous polarization displacements than Pb, but the Pb-O covalence seems to be weakened compared to the potassium counterpart Pb2KNb5O15 (PKN), which may account for the similar Curie temperature and uniaxial NTE behavior for PAN and PKN. Powder second harmonic generation (SHG) measurement indicates that PAN displays a moderate SHG response of ∼0.2 × LiNbO3 (or ∼100 × α-SiO2) under 1064 nm laser radiation. The magnitudes of the local dipole moments in NbO6 and PbOx polyhedra were quantified using bond-valence approach. We show that the SHG response stems from the superposition of dipole moments of both the PbO(x) and NbO6 polyhedra.

Oxygen storage properties and catalytic activity of layer-ordered perovskites BaY1 − xGdxMn2O5 + δ

Crystal structure, oxygen storage-related and preliminary anaerobic methane combustion studies were conducted for BaY1−xGdxMn2O5+δ (0, 0.25, 0.5, 0.75 and 1) series of oxides prepared by a sol–gel method. All samples were found to possess layered-type A-site cation ordering, with the unit cell volume linearly dependent on the average radius of Y1−xGdx for both the reduced and the oxidized materials. The oxygen content in the temperature range of 400°C–600°C indicates change on the order of 1 atomic mole, occurring when the sample's surrounding atmosphere was changed from air to 5vol.%H2 in Ar. The time dependence of the reduction shows activated character on temperature, with an activation energy, which seems to be related to the oxygen diffusion in the bulk of the materials. Initial data concerning methane combustion in oxygen-free conditions show promising catalytic activity of BaYMn2O6 at elevated temperatures.

Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositions in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. The computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.