Double Perovskite Oxides Research Articles

Electron holography observation of individual ferrimagnetic lattice planes.

Atomic-scale observations of a specific local area would be considerably beneficial when exploring new fundamental materials and devices. The development of hardware-type aberration correction1,2 in electron microscopy has enabled local structural observations with atomic resolution3-5 as well as chemical and vibration analysis6-8. In magnetic imaging, however, atomic-level spin configurations are analysed by electron energy-loss spectroscopy by placing samples in strong magnetic fields9-11, which destroy the nature of the magnetic ordering in the samples. Although magnetic-field-free observations can visualize the intrinsic magnetic fields of an antiferromagnet by unit-cell averaging12, directly observing the magnetic field of an individual atomic layer of a non-uniform structure is challenging. Here we report that the magnetic fields of an individual lattice plane inside materials with a non-uniform structure can be observed under magnetic-field-free conditions by electron holography with a hardware-type aberration corrector assisted by post-digital aberration correction. The magnetic phases of the net magnetic moments of (111) lattice planes formed by opposite spin orderings between Fe3+ and Mo5+ in a ferrimagnetic double-perovskite oxide (Ba2FeMoO6) were successfully observed. This result opens the door to direct observations of the magnetic lattice in local areas, such as interfaces and grain boundaries, in many materials and devices.

Effective suppression of surface cation segregations on double perovskite oxides through entropy engineering

Cation segregation on cathode surfaces plays a key role in determining the activity and operational stability of solid oxide fuel cells (SOFCs). The double perovskite oxide PrBa0.8Ca0.2Co2O5+δ (PBCC) has been widely studied as an active cathode but still suffer from serious detrimental segregations. To enhance the cathode stability, a PBCC derived A-site medium-entropy Pr0.6La0.1Nd0.1Sm0.1Gd0.1Ba0.8Ca0.2Co2O5+δ (ME-PBCC) oxide was prepared and its segregation behaviors were investigated under different conditions. Compared with initial PBCC oxide, the segregations of BaO and Co3O4 on the surface of ME-PBCC material are significantly suppressed, especially for Co3O4, which is attributed to its higher configuration entropy. Our results also confirm the improved electrochemical performance and structural stability of ME-PBCC material, enabling it as a promising cathode for SOFCs.

Structure, Electronic, Optical, Magnetic and Magnetocaloric Properties of Sm2CuMnO6 Double Perovskite Nanomaterial

This study explores the structural, microstructural, optical, and magnetic characteristics of double perovskite oxide Sm2CuMnO6. The sample is prepared in the monoclinic phase with space group P21/n using the auto-combustion method. The crystal structure exhibits distortion and tilting. First-principles calculations are conducted using the density-functional theory framework, focusing on electronic structures and density of states. The average crystallite size, particle size and grain size of the sintered sample are 34.42 nm, 36.15 nm and 475 nm respectively. The sample exhibits a direct band gap energy of 1.96 eV. Analysis of the X-ray photoelectron spectra indicates the presence of Sm3+, Cu2+, and Mn3+/Mn4+ ions in the sample. The DC magnetization study reveals a Curie temperature (Tc) of 50 K for the sample. A non-metallic state resembling a spin glass is detected below 15 K, arising from the competition between antiferromagnetic and ferromagnetic interactions. The maximum value of isothermal magnetic entropy, the relative cooling power and heat capacity are 1.4 J.kg–1.K–1, 100.2 J.kg–1, and 1.35 J.kg–1.K–1 at a field change of 70 kOe respectively. The value of Temperature Averaged Entropy Change is 1.36 J.kg−1.K−1 and 1.29 J.kg−1.K−1 for a temperature span of 10 K and 40 K at a field change of 70 kOe.

Enhancing the TiO2 light harvesting ability boosted by Sr2FeTeO6 additives in DSSCs

In this work, novel surface defected lead-free double perovskite oxide (Sr2FeTeO6) has been introduced in dye sensitized solar cells (DSSCs) for the first time. The Sr2FeTeO6 material prepared by solid state method treated at 1200 °C. The DSSC was performed with varying weight percentage (0.01 wt%, 0.03 wt%, 0.05 wt%) of Sr2FeTeO6 additives incorporated with titanium di-oxide (TiO2) photoanode for light harvesting under AM 1.5 solar irradiation. The inorganic double perovskite oxide material as promising additive would be in the future developing 3rd generation solar cell technologies.

Enhancing Trifunctional Electrocatalytic Activities via Lanthanide Modulation in Fe–Co-Based Double Perovskite Oxides

Enhancing Trifunctional Electrocatalytic Activities via Lanthanide Modulation in Fe–Co-Based Double Perovskite Oxides

Doping-Induced piezoelectricity in Ba2Nb2-xFexO6-δ double perovskite oxides for efficient hydrogen peroxide production via piezocatalysis in pure water

Piezocatalysis has emerged as a sustainable alternative for hydrogen peroxide production. However, the current development of efficient piezocatalysts is predominantly focusing on those conventional piezoelectric ceramic oxides with high permittivity and limited catalytic activities. Therefore, innovative approaches to develop novel piezocatalysts in particular from these outstanding paraelectric semiconductors are highly required. In this work, by employing a feasible doping strategy, robust piezoelectric property is created on the Ba2Nb2-xFexO6-δ double perovskite oxides, typically characterized by a stable paraelectric cubic structure. Optimum Fe doping not only intensifies the double perovskite phase but also inspires a phase transition from a centrosymmetric cubic to a piezoelectric tetragonal phase, thereby achieving desirable piezoelectricity and enabling a series of favorable physical properties including redox activity, active sites of anion defects, reduced bandgap, and increased free charge density. All these are important factors to enhance piezocatalytic activity. As a result, Ba2NbFeO6-δ achieved by the optimum Fe doping demonstrated exceptional piezocatalytic H2O2 yield of 512 and 690 µmol g-1 h−1 under atmosphere and oxygen-purging conditions, respectively, without the presence of any sacrificial agents. Mechanistic investigations reveal that both water oxidation and oxygen reduction involve in the H2O2 production, wherein piezopotential plays a critical role not only in facilitating the charge carrier separation and transportation but also in modulating the band structure to enhance the catalyst redox capacity. This study offers a feasible and universal strategy for the design of novel piezocatalysts, expanding the windows for catalyst selection for piezocatalysis.

Ca-Doping Cobalt-Free Double Perovskite Oxide as a Cathode Material for Intermediate-Temperature Solid Oxide Fuel Cell.

Mixed oxygen ion and electron-conducting materials are viable cathodes for solid oxide fuel cells due to their excellent oxygen transport kinetics and mixed electrical conductivity, which ensure highly efficient operation at low and medium temperatures. However, iron-based double perovskite oxides usually exhibit poor electrocatalytic activity due to low electron and oxygen ion conductivity. In this paper, Ca is doped in PrBaFe2O5+δ A-site to improve the electrochemical performance of PrBaFe2O5+δ. Results show that replacing Pr with Ca does not change the crystal structure, and the Ca doping effectively increases the adsorbed oxygen content and accelerates the migration and diffusion rate of O2- to the electrolyte|cathode interface. The polarization resistance of the symmetric cell PC0.15BF|CGO|PC0.15BF is 0.033 Ω·cm2 at 800 °C, which is about 56% lower than that of PBF, confirming the enhancement of the mixed conduction of oxygen ions and electrons. In addition, the anode-supported single cell has a peak power density of 512 mW·cm-2 at 800 °C.

Turning bad into good: A medium-entropy double perovskite oxide with beneficial surface reconstruction for active and robust cathode of solid oxide fuel cells

The cathodes of solid oxide fuel cells (SOFCs) often suffer from detrimental cation segregations and associated impurities poisoning, leading to insufficient electroactivity and poor stability. Here we developed a medium-entropy double perovskite GdBa(Co1.2Mn0.2Fe0.2Ni0.2Cu0.2)O5-δ (ME-GBCO) for promising SOFC cathode. The increased configuration entropy can effectively tailor the surface composition with in situ formed active BaCoO3-δ (BCO) species, rather than inert and deleterious BaOx segregation on parent GdBaCo2O5-δ (GBCO) surface. Accordingly, the layered ME-GBCO cathode with beneficial surface reconstruction exhibited not only high oxygen reduction activity but excellent durability against CO2 impurity, enabling it a very attractive cathode for intermediate temperature SOFCs (IT-SOFCs). Our study provides a new idea for development of efficient and durable cathodes via configurational entropy induced rational surface reconstruction.

Investigation of structure, dielectric, thermistor, and optical properties study of an eco-friendly double perovskite for photovoltaic and optoelectronic applications: CaLiFeWO6

Double-perovskite oxides have received interest recently because of their appealing photovoltaic and optoelectronic properties for promising applications. In this paper, we demonstrate the synthesis (solid-state reaction) as well as characterization study of an eco-friendly novel double perovskite CaLiFeWO6. Preliminary investigation of X-ray diffraction (XRD) data reveals a monoclinic structure. Micro-lattice strain and average size of crystallite are found to be 0.000564 and 86 nm. The distribution of grains and elemental composition of the sintered sample was recorded using scanning electron microscope (SEM) cum energy dispersive X-ray spectroscopy (EDX). Raman scattering spectroscopy is tailored to study the vibrational Raman modes involved in the sample. The optical analysis was investigated by employing UV visible spectroscopy and used to obtain bandgap energy within the range for optoelectronic device applications. To understand the electrical behavior of the synthesized double perovskite, the authors conducted both low and high-frequency dielectric measurements and utilized impedance spectroscopy. The conductivity behavior in the studied material follows Jonscher's power law. Resistance versus temperature data supports the concept of negative temperature coefficient (NTC) thermistors for temperature sensors and temperature control systems. Polarization-electric field supports the possibility of ferroelectric behavior, which opens the door to a wide range of technological advancements and innovations in various fields.

Probing the metallic state, magnetic anisotropy, and large Curie temperature in CaCuFeReO[formula omitted]: Strain engineering

Rhenium-based double perovskite oxides (DPOs) are a particularly fascinating class of materials because of high carrier spin polarization, large magnetic anisotropy energy (MAE), and complex electrical behavior along with high Curie temperature (TC). Herein, we discussed the impact of biaxial ([110]) strain ranging from −5% to ＋ 5% along the ab-plane on the electronic and magnetic properties of CaCuFeReO6 (CCFRO) DPO using ab-inito calculations. The unstrained system exhibits a ferrimagnetic (FiM) spin ordering as an energetically stable magnetic ground state due to electron hopping between Fe+3/Re+5t2g and Cu+2eg orbitals along with a metallic electronic state. Moreover, [010] (b-axis) is the magnetic easy axis that produces the MAE of 5.36 meV, giving a giant MAE constant of 1.97×107 erg/cm3. The evaluated partial spin-magnetic moment on the Cu1/Cu2/Fe/Re ion is 0.14/0.44/4.04/−0.64μB, where “−” sign on the Re moment means that its spin is antiparallel to the other ions, verifying the FiM ordering in the system. Also, the eg, t2g/eg, and t2g orbital characteristics of Cu+2, Fe+3, and Re+5 ions are visible in the spin-magnetization density iso-surfaces plots, respectively. Using the classical Heisenberg model, the computed TC for the unstrained structure is 576 K, which is quite close to the experimentally reported value of 567 K. In addition, it is shown that the FiM metallic behavior in the motif is robust against biaxial ([110]) strain within the considered range. It has also been revealed that TC increased to 5.73%/3.30% for the considered range of −5% compressive/＋5% tensile strain due to improved structural distortions.

Experimental and Computational Insights into the Catalytic Mechanism of Y1-xBaxCoO3-δ Perovskite Oxides with a Controlled Crystal Structure.

The crystal structure of Co-based perovskite oxides (ACoO3) can be controlled by adjusting the A-site elements. In this study, we synthesized Y1-xBaxCoO3-δ (x = 0, 0.5, and 1.0) via a coprecipitation method and investigated their CO oxidation performances. YCoO3 (x = 0; cubic perovskite oxide; Pbnm) shows a higher catalytic performance than Y0.5Ba0.5CoO2.72 (x = 0.5; A-site-ordered double perovskite oxide; P4/nmm), which exhibits high oxygen nonstoichiometric properties, and BaCoO3 (x = 1.0; hexagonal perovskite oxide; P63/mmc), which contains high-valent Co4+ species. To elucidate the reaction mechanism, we conducted isotopic experiments with CO and 18O2. The CO oxidation reaction on YCoO3 proceeds via the Langmuir-Hinshelwood mechanism, which is a surface reaction of CO and O2 gas that does not utilize lattice oxygen. Because of the significantly smaller specific surface area of YCoO3 compared with that of the reference Pt/Al2O3, the bulk features of the crystal structures affect the catalytic reaction. When density functional theory is applied, YCoO3 clearly exhibits semiconducting properties in the ground state with the diamagnetic t2g6eg0 states, which can translate to a magnetic t2g5eg1 configuration upon excitation by a relatively low energy of 0.64 eV. We propose that the unique nature of YCoO3 activates oxygen in the gas phase, thereby enabling the smooth oxidation of CO. This study demonstrates that the bulk properties originating from the crystal structure contribute to the catalytic activity and reaction mechanism.

Electronic, magnetic, elastic and optical properties of Ba2CoTaO6 double perovskite oxide: A DFT study

In this study, the computational functionals GGA and mBj of density functional theory (DFT) were employed to explore the electronic structure of tantalum based double perovskite oxide Ba2CoTaO6. Computed tolerance (t) and octahedral (µ) factors deduce the cubic stability of the perovskite crystal. Negative formation energy indicates that the system is thermodynamically stable. The elastic constants satisfy the conditions for cubic stability and the Pagh’s index (B/G) evinces the brittle nature. The band structure and total density of states reveal the half-metallic nature with a 4.7 eV insulator indirect energy band gap at the Fermi level in the spin up direction. An integer-valued (4µB) magnetic moment is observed to favor the half-metallic ferromagnetism in the double perovskite oxide Ba2CoTaO6. Optical properties play a significant role in the design and functionality of optical devices and systems. In this aspect, the two parts of the dielectric function (real and imaginary) and the related parameters have been explored. The observed properties provide insights into possible applications of this system in spintronics and optoelectronics.

Preparation and characterization of Pr1-xNdxBaFe2O5+δ nanofiber cathodes for solid oxide fuel cells

Double perovskite oxide Pr1-xNdxBaFe2O5+δ (PNBFx, x = 0.0–0.3) nanofiber were prepared using electrospinning and were evaluated as cathodes for solid oxide fuel cells (SOFCs). The crystalline structure, microstructure, and electrochemical performance of PNBFx were thoroughly investigated and discussed. The PNBFx nanofiber cathodes obtained after sintering at 800 °C crystallized in a tetragonal structure with the space group P4/mmm and had good chemical compatibility with SDC electrolytes at 900 °C for 4 h. Nd doping was found to increase the lattice parameter, while the average valence of praseodymium and iron content increased steadily in PNBFx. The Pr0.8Nd0.2BaFe2O5+δ (PNBF02) nanofiber cathode exhibited the best performance with a polarization resistance (Rp) of 0.072 Ω cm2 at 750 °C. When PNBF02 nanofiber was used as a single-cell cathode, the peak power density reached 1.52 W cm2 at 750 °C. All results indicate that double perovskite PNBF02 is a promising cathode material for SOFCs.

The structural, stability, electronic, optical and thermodynamic properties of Ba2AsXO6（X = V, Nb, Ta）double perovskite oxides: A First-Principles study

In this paper, the structural, mechanical, electronic, optical and thermodynamic properties of Ba2AsXO6 (X = V, Nb, Ta) double perovskite oxides have been studied based on the first principles of density functional theory. By calculating some parameters such as Goldsmith’s tolerance factor (tG), octahedral factor (µ), Bartel’s tolerance factor (τ), formation energy, binding energy and elastic constants, it is found that these double perovskite oxides have the potential for stable existence. In addition, Ba2AsXO6 (X = V, Nb, Ta) is an anisotropic material, in which Ba2AsVO6 is brittle, Ba2AsNbO6 and Ba2AsTaO6 are ductile. The electronic properties of the materials show that Ba2AsVO6 and Ba2AsNbO6 are indirect bandgap semiconductors with a band gap of 1.676 eV and 2.654 eV respectively, while Ba2AsTaO6 is direct bandgap semiconductor with a band gap of 3.252 eV. The optical properties revealed that these perovskites exhibit favorable far-ultraviolet light absorption characteristics. The thermodynamic properties show that the specific heat capacity of these double perovskite oxides reaches the Dulong-Petit limit at around 800 K. These results indicate that Ba2AsXO6 (X = V, Nb, Ta) double perovskite oxides have broad application prospects in the fields of thermoelectricity and optoelectronics. Furthermore, these results also provide a valuable theoretical basis for their future experimental synthesis.

A medium-entropy engineered double perovskite oxide for efficient and CO2-tolerant cathode of solid oxide fuel cells

Developing highly active and robust cathodes remains challenging for solid oxide fuel cells (SOFCs). Therefore, we report an A-site medium-entropy double perovskite oxide PrBa0.5Sr0.25Ca0.2Ce0.05Co2O5+δ (PBSCCC) and its electrocatalytic activity and CO2 tolerance property are systematically probed. The PBSCCC cathode exhibits excellent oxygen reduction reaction (ORR) activity with a low polarization resistance of 0.027 Ω cm2 at 700 °C. More importantly, compared to PrBaCo2O5+δ (PBC) and PrBa0.8Ca0.2Co2O5+δ (PBCC) oxides, its CO2 resistance is prominently enhanced with significantly less BaCO3 and Co3O4 impurities formed. The superior ORR performance and structure stability are mainly attributed to its high electrical conductivity and significantly reduced surface cation segregations. Our results show that the potential of PBSCCC as a cathode material for SOFCs is enormous and also prove the rationality and feasibility of entropy engineering for cathode development.

J[formula omitted] Mott-insulating to S = 0 metal transition in Ce@Y-doped Y[formula omitted]NiIrO[formula omitted]

Double perovskite oxides (DPOs) having 3d-5d electrons provide an optimal field to investigate the entanglement between spin–orbit coupling and electron correlation, displaying unusual physical phenomena. Here, we predicted a large magnetic anisotropy energy (MAE) constant of 1.7 × 108 erg/cm3 in a pristine ferrimagnetic (FiM) Y2NiIrO6 DPO with the magnetic easy axis of the monoclinic b-axis. The estimated Curie temperature (TC) of 198 K using the Heisenberg model agrees well with the experimentally observed value of 192 K. Antiferromagnetic coupling between Ni and Ir ions is confirmed, which supports the FiM as a ground state of the system. Furthermore, it is found that the motif displays a Mott-insulating nature because of the exceptional Jeff=12 state of Ir+4 with an effective magnetic moment (meff.) of ∼2.19μB/u.c. (per unit cell), where Ni/Ir ion contains 1.68/−0.49μB. Upon substitution of Ce at Y-site (Ce@Y), few states grow at the Fermi level which belongs to Ir 5d orbitals and meff. enhanced to 3.13 μB/u.c., while FiM survives as a ground state. Along with this, Ni moment remains unchanged, while it substantially reduces to −0.10μB for Ir ion which leads to be in a ＋ 3 (5d6) state with S = 0 and almost persists in the paramagnetic phase. Due to the larger atomic radii of Ce than that of Y, the Ce@Y-doped motif exhibits a large structural distortion as compared to the pristine one, which increases the MAE and TC values simultaneously. Furthermore, calculated enthalpies of formation, distinct elastic constants, and phonon dispersion spectrums ensure the thermodynamic, mechanical, and dynamical stability of the pristine as well as the Ce@Y-doped system, respectively.

Effects of lanthanide doping on the electrode properties and exsolution behavior of A-site deficient Sr1.9Fe1.3Ni0.2Mo0.5O6-δ double perovskites

Double perovskite oxides of the Sr2Fe1.5Mo0.5O6-δ class are promising electrodes for Solid Oxide Fuel Cells (SOFCs) and Electrolyzers (SOECs) due to their outstanding electrochemical properties and durability. Additionally, their physicochemical properties can be tuned by B-site cation doping, namely, by partially substituting Fe cations with other transition metals such as Ni, Co, Mn, or Cu. This also allows the grain-surface functionalization with metallic alloyed nanocatalysts upon reduction driven by the exsolution phenomena, leading to higher electrocatalytic activity and resistance against sintering and coking. Traditionally, A-site deficiency has been employed to improve the amount of exsolved nanoparticles and, thereby, increase the number of Triple Phase Boundaries in the electrode. However, in Ni-doped non-stoichiometric double perovskite materials (e.g., Sr1.9Fe1.3Ni0.2Mo0.5O6-δ), A-site deficiency results in undesired NiO phase segregations. This, in turn, lowers the number of exsolvable cations, decreasing the number of metallic nanocatalysts compared to the stoichiometric compound. In this work, the impact of A-site doping with lanthanides (viz. Gd, La, Nd, and Pr) on the exsolution ability and electrochemical properties of non-stoichiometric Sr1.9Fe1.3Ni0.2Mo0.5O6-δ was evaluated. The results indicate that lanthanide doping enhances the conductivity of the double perovskites both in oxidizing and reducing atmospheres. In addition, lanthanide dopants that slightly destabilize the cubic structure also improve the exsolution dispersion, which decreases with increasing the double perovskite cell volume. These results illustrate how to design more efficient and durable electrocatalysts by modifying the double perovskite structure with A-site dopants.

Boosting the electrocatalytic activity of NdBaCo2O5+δ via calcium co-doping as bifunctional oxygen electrodes for reversible solid oxide cells

The oxygen electrode of the solid oxide cells (SOCs) operates under an oxidizing atmosphere. Lattice shrinkage in a high oxygen partial pressure environment results in cation misalignment, leading to a decline in performance. Addressing the drawbacks associated with A-site cation mismatch in LnBaCo2O5+δ double perovskite oxides for reversible solid oxide cells (RSOCs) oxygen electrodes, a novel calcium ion co-doping strategy is proposed. This approach effectively mitigates A-site cation segregation and enhances stability. The glycine-nitrate method was employed to synthesize Nd0.8Ca0.2Ba1−xCaxCo2O5+δ (x = 0–0.2) layered double perovskites oxides co-doped with calcium ions, denoted as NCBCC. NCBCC exhibits excellent compatibility with commonly used electrolytes. The doping of calcium co-doped in NdBaCo2O5+δ decreases the thermal expansion coefficient and improves the electron transfer characteristics. The sample with x = 0.1 exhibited an area-specific resistance (ASR) of 0.024 Ω cm2 when operated at a temperature of 800 °C in air. In the solid oxide fuel cell mode, employing x = 0.1 as an oxygen electrode, the maximum power density achieved was 766 mW cm−2 at 800 °C. In the solid oxide electrolysis cell mode, operating with CO2 and steam at an electrolysis voltage of 1.5 V and a temperature of 800 °C, the corresponding current densities were −1.51 and −1.85 A cm−2, respectively. The incorporation of calcium ions into layered perovskite oxides offers a promising strategy to enhance the performance of oxygen electrodes in RSOCs.

Magnetoelastic Coupling Evidence by Anisotropic Crossed Thermal Expansion in Magnetocaloric RSrCoFeO6 (R = Sm, Eu) Double Perovskites.

Double perovskite oxides, characterized by their tunable magnetic properties and robust interconnection between the lattice and magnetic degrees of freedom, present an enticing foundation for advanced magnetic refrigeration materials. Herein, we delve into the influence of rare-earth elements on RSrCoFeO6 (R = Sm, Eu) disordered double perovskites by examining their structural, electronic, magnetic, and magnetocaloric properties. Temperature-dependent synchrotron X-ray diffraction analysis confirmed the stability of the orthorhombic phase (Pnma) across a wide temperature range. X-ray photoemission spectroscopy revealed that both Sm and Eu are in the 3+ state, whereas multiple states for Co2+/3+ and Fe3+/4+ are identified. The magnetic investigation and magnetocaloric effect (MCE) analysis brought to light the presence of a long-range antiferromagnetic (AFM) order with a second-order phase transition (SOPT) in both samples. The maximum magnetic entropy change ΔSMmax was approximately 0.9 J/kg K for both samples at applied field 0-7 T, manifesting prominently above Neel temperatures TN ≈ 93 K (Sm) and 84 K (Eu). Nevertheless, different relative cooling powers (RCP) of 112.6 J/kg (Sm) and 95.5 J/kg (Eu) were observed. A detailed analysis of the temperature-dependent lattice parameters shed light on a distinct magnetocaloric effect across the magnetic transition temperature, unveiling an anisotropic thermal expansion [αV = 1.41 × 10-5 K-1 (Sm) and αV = 1.54 × 10-5 K-1 (Eu)] wherein the thermal expansion axial ratio αbSm/αbEu = 0.61 became lower with increasing temperature, which suggests that the Eu sample experiences a greater thermal expansion in the b-axis direction. At the atomic bonding level, the evidence for magnetoelastic coupling around the magnetic transition temperatures TN was found through the anomalies along the average Co/Fe-O bond distance, formal valence, octahedral distortion, as well as an anisotropic lattice expansion.

Structural mode coupling in perovskite oxides using hypothesis-driven active learning

Finding the ground-state structure with minimum energy is paramount to designing any material. In ABO3-type perovskite oxides with Pnma symmetry, the lowest energy phase is driven by an inherent trilinear coupling between the two primary order parameters such as rotation and tilt with antiferroelectric displacement of the A-site cations as established via hybrid improper ferroelectric mechanism. Conventionally, finding the relevant mode coupling driving phase transition requires performing first-principles calculations which is computationally time-consuming as well as expensive. It involves following an intuitive iterative hit and trial method of (a) adding two or multiple mode vectors, followed by (b) evaluating which combination would lead to the ground-state energy. In this study, we show how a hypothesis-driven active learning framework can identify suitable mode couplings within the Landau free energy expansion with minimal information on amplitudes of modes for a series of double perovskite oxides with A-site layered, columnar and rocksalt ordering. This scheme is expected to be applicable universally for understanding atomistic mechanisms derived from various structural mode couplings behind functionalities, for e.g. polarization, magnetization and metal–insulator transitions.