Here, the first-principles predictions on the structural stability, magnetic behavior and electronic structure of B-site ordered double perovskite Nd$_{2}$FeCrO$_{6}$ have been reported. Initially, the ground state of the parent single perovskites NdCrO$_{3}$ and NdFeO$_{3}$ have been studied to determine the relevant Hubbard U parameter to investigate the properties of Nd2CrFeO6. The thermodynamic, mechanical, and dynamic stability analyses suggest the possibility of the synthesis of Nd$_{2}$FeCrO$_{6}$ double perovskite at ambient pressure. The compound shows ferrimagnetic (FiM) nature with 2 $μ$B net magnetic moments and the magnetic ordering temperature has been estimated to be $\sim$265 K. Electronic structure indicates higher probability of direct photon transition over the indirect transition with a bandgap of $\sim$1.85 eV. Additional effect of Nd (4f) spin and spin-orbit coupling (SOC) on the band edges have been found to be negligible for this 4f-3d-3d spin system. This first-principles investigation predicts that due to the ferrimagnetic nature and significantly lower bandgap compared to its antiferromagnetic parent single perovskites, B-site ordered Nd$_{2}$FeCrO$_{6}$ double perovskite could be a promising material for spintronic and visible-light-driven energy applications.
Lead-free double perovskites are overtaking single perovskites as solar harvesting materials due to their superior stability, excellent catalytic efficiency and minimal toxicity. In this investigation, we have synthesized double perovskite Gd$_{2}$FeCrO$_{6}$ (GFCO) nanoparticles for the first time via a facile sol-gel technique to investigate their structural, magnetic and optical properties. The double perovskite GFCO crystallized in monoclinic structure with P2$_1$/n space group. The Fe/Cr-O bond length was calculated as $\sim$1.95 angstrom from the Raman spectrum which was consistent with …
We have synthesized Gd$_{2}$FeCrO$_{6}$ (GFCO) double perovskite which is crystallized in a monoclinic structure with P2$_{1}/$n space group. The UV-visible and photoluminescence spectroscopic analyses confirmed its direct bandgap semiconducting nature. Employing experimentally obtained structural parameters in first-principles calculation, we report the spin-polarized electronic band structure, charge carrier effective mass, density of states, electronic charge density distribution and optical absorption property of the GFCO double perovskite. The effects of on-site d-d Coulomb interaction en…
We have investigated the effect of epitaxial strain on the magnetic properties and $B$-site cation ordering in multiferroic Bi$_2$FeCrO$_6$ (001) thin films using a density-functional theory approach. We find that in thin films with rock-salt ordering of Fe and Cr the ground state is characterised by C-type anti-ferromagnetic (AFM) order. This is in contrast to the bulk form of the material which was predicted to be a ferrimagnet with G-type AFM order. Furthermore, the cation ordered thin-films undergo a transition with epitaxial strain from C to A-type AFM order. Other magnetic orders appear …
Double perovskite Bi$_2$FeCrO$_6$, related with BiFeO$_3$, is very interesting because strong ferroelectricity and high magnetic Curie temperature beyond room temperature are observed in it. However, existing density-functional-theory (DFT) studies, using pseudo-potentials, produce metallic ground state under the local density approximation (LDA) and need LDA+U method to yield needed nonmetallic ground state, resulting in low magnetic Curie temperature (below 130 K). Here, we optimize its crystal structure and then investigate its electronic structure and magnetic and optical properties by com…
The impact of ordered vacancies on the dynamic stability of perovskites is investigated under the $\textit{ab initio}$ framework with a focus on cubic BaFeO$_{3}$ ($Pm\bar{3}m$) and vacancy-ordered monoclinic BaFeO$_{2.67}$ ($P2_{1}/m$). The harmonic approximation shows that both structures are dynamically unstable at 0 K. For the monoclinic structure, the instability is related to rotational distortions of the Fe coordination tetrahedra near the ordered vacancies. $\textit{Ab initio}$ molecular dynamics simulations in combination with the introduced structural descriptor demonstrate that both…
We report x-ray diffraction, resistivity, thermopower, and magnetization of Sr3ErMn4-xGaxO10.5-d, in which A-site ordered tetragonal phase appears above x=1, and reveal that the system exhibits typical properties seen in the antiferromagnetic insulator with Mn3+. We succeed in preparing both A-site ordered and disordered phases for x=1 in different preparation conditions, and observe a significant decrease of the resistivity in the disordered phase. We discuss possible origins of the decrease focusing on the dimensionality and the disordered effect.
For decades, numerous attempts have been made to produce polar oxynitride perovskites, where some of the oxygen are replaced by nitrogen, but a polar ordered oxynitride has never been demonstrated. Caracas and Cohen studied possible ordered polar oxynitrides within density functional theory (DFT) and found a few candidates that were predicted to be insulating and at least metastable. YSiO2N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSiO2N by using a combination of a diamond anvil cell and in…
The complex perovskite Ba2CoTeO6 (BCTO) has been synthesised, and the crystal structure and magnetic properties have been investigated using a combination of X-ray and neutron powder diffraction, electron microscopy and dielectric, calorimetric and magnetic measurements. It was shown that at room temperature this compound adopts the 6L-trigonal perovskite structure, space group P-3m (N 164) (a= 5.7996(1)Å, c=14.2658(3)Å). The structure comprises dimers of face-sharing octahedra as well as octahedra which share only vertices with their neighbours. A long-range antiferromagnetically ordered stat…
The possibility to segregate cobalt and iron in a single perovskite, at a nanoscale in the form of layers has been investigated, using sol gel technic synthesis. Quite remarkably, it is shown that such a nanoscale ordering, which can only be detected by a combined HAADF-STEM and EELS study, has a significant impact upon the magnetic properties of this SmFe0.5Co0.5O3 oxide. This suggests that careful nanoscale characterization of oxides will be necessary in the future before proceeding to a viable interpretation of their physical properties, at least in the field of magnetism.
In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.
The layered perovskite YBaCuFeO5 (YBCFO) is able to adopt chiral magnetic order up to unexpectedly high temperatures, paving the way to strong magnetoelectric coupling at room temperature. In this perovskite A-site cations are fully ordered whereas the occupancy of the B-sites strongly depend on the preparation process. Though the structure is not geometrically frustrated, the presence of partial Fe3+/Cu2+ disorder at the B-sites produces magnetic frustration. In an effort to increase the spin-orbit coupling in the system, we have synthesized and studied YBaCuFe0.95Mn0.05O5 in single crystal f…
Ferromagnetic insulators (FMIs) are one of the most important components in developing dissipationless electronic and spintronic devices. However, since ferromagnetism generally accompanies metallicity, FMIs are innately rare to find in nature. Here, novel room-temperature FMI films are epitaxially synthesized by deliberate control of the ratio of two B-site cations in the double perovskite Sr2FeReO6. In contrast to the known ferromagnetic metallic phase in stoichiometric Sr2FeReO6, a FMI state with a high Curie temperature (Tc~400 K) and a large saturation magnetization (MS~1.8 μB/f.u.) is fo…
The electronic orbital characteristics at the band edges plays an important role in determining the electrical, optical and defect properties of perovskite photovoltaic materials. It is highly desirable to establish the relationship between the underlying atomic orbitals and the optoelectronic properties as a guide to maximize the photovoltaic performance. Here, using first-principles calculations and taking anion ordered Ruddlesden-Popper (RP) phase halide perovskites Cs$_{n+1}$Ge$_n$I$_{n+1}$Cl$_{2n}$ as an example, we demonstrate how to rationally optimize the optoelectronic properties (e.g…
Rare earth perovskite cobaltites are increasingly recognized as materials of importance due to rich physics and chemistry in their ordered-disordered structure for the same composition. Apart from colossal magnetoresistance effect, like manganites, the different forms of cobaltites exhibit interesting phenomena including spin, charge and orbital ordering, electronic phase separation, insulator-metal transition, large thermoelectric power at low temperature. Moreover, the cobaltites which display colossal magnetoresistance effect could be used as read heads in magnetic data storage and also in …
Increasing demands for electric field-tunable electric, magnetic, and orbital (EMO) materials has renewed interests in ferroelectricity and its coupling to EMO properties in complex perovskite oxides. The historic design strategy to achieve a spontaneous polarization involves the incorporation of second-order Jahn-Teller (SOJT) active cations. The challenge, however, is that this mechanism is limited to specific chemistries and the polar distortions that arise are largely decoupled from EMO properties, limiting their use as field-tunable multifunctional technology materials. Here we report the…
We report a first-principles study of Bi-based 3$d$-5$d$ ordered double perovskite oxides (A$_2$BB$^\prime$O$_6$) with a 3$d$ atom (Fe) at the B-site and 5$d$ atoms (Re,Ir) at the B$^\prime$-site while keeping highly polarizable ions (Bi$^{3+}$) at the A-site. We find that, under coherent heteroepitaxy, Bi$_2$FeReO$_6$} exhibits a strain-driven anti-ferromagnetic insulator to ferrimagnetic semi-metal transition, while Bi$_2$FeIrO$_6$ shows correlation driven ferromagnetic insulator to ferrimagnetic half-metal transition with calculated magnetic moments of 5 $μ_B$/f.u. and 3 $μ_B$/f.u., respect…
Investigation of the oxygen-deficient 112-type ordered oxides of the type LnBaCoMnO5+δ(Ln = Nd, Eu) evidences certain unusual magnetic behavior at low temperatures, compared to the LnBaCo2O5+δcobaltites. One observes that the substitution of manganese for cobalt suppresses the ferromagnetic state and induces strong antiferromagnetic interactions. Importantly, NdBaCoMnO5.9 depicts a clear paramagnetic to antiferromagnetic type transition around 220 K, whereas for EuBaCoMnO5.7 one observes an unusual magnetic behavior below 177 K which consists of ferromagnetic regions embedded in an antiferroma…
The complex perovskite Pb2CoTeO6 (PCTO) has been prepared as polycrystalline powders by solid state reaction route, and the crystal structure and magnetic properties have been investigated using a combination of X-ray and neutron powder diffraction, electron microscopy, dielectric, calorimetric and magnetic measurements. It was shown that at room temperature this compound adopts a trigonal perovskite structure, space group R-3 (a= 5.6782(1)Å, c= 13.8552(3)Å). The compound undergoes a number of temperature-induced phase transitions and adopts four different structures in the temperature range 5…
The structures of the recently reported ordered perovskites SrLa(FeTi)O6 and BaLa(FeTi)O6 have been revisited using Rietveld analysis of the powder x-ray diffraction data. Our studies clearly show that earlier authors have incorrectly reported the tetragonal structure in the I4/m space group for SrLa(FeTi)O6 and the cubic structure in the Fm3m space group for BaLa(FeTi)O6. The correct structure is found to be orthorhombic in the Pnma space group for SrLa(FeTi)O6 while cubic in the Pm3m space group for BaLa(FeTi)O6. Thus the BaLa(FeTi)O6 is not an ordered double perovskite as the occupancies of…
Magnetic insulators have been intensively studied for over 100 years, and they, in particular ferrites, are considered to be the cradle of magnetic exchange interactions in solids. Their wide range of applications include microwave devices and permanent magnets . They are also suitable for spintronic devices owing to their high resistivity, low magnetic damping, and spin-dependent tunneling probabilities. The Curie temperature is the crucial factor determining the temperature range in which any ferri/ferromagnetic system remains stable. However, the record Curie temperature has stood for over …
We report and compare the structural, magnetic, and optical properties of ordered La2NiMnO6 thin films and its disordered LaNi0.5Mn0.5O3 counterpart. An x-ray diffraction study reveals that the B-site Ni/Mn ordering induces additional XRD reflections as the crystal symmetry is transformed from a pseudocubic perovskite unit cell in the disordered phase to a monoclinic form with larger lattice parameters for the ordered phase. Polarized Raman spectroscopy studies reveal that the ordered samples are characterized by additional phonon excitations that are absent in the disordered phase. The appear…
Ba2CoWO6 (BCoW) has been synthesized in polycrystalline form by solid state reaction at 1200C. Structural characterization of the compound was done through X-ray diffraction (XRD) followed by Rietveld analysis of the XRD pattern. The crystal structure is cubic, space group Fm-3m (No 225) with the lattice parameter, a=8.210A. Optical band-gap of the present system has been calculated using the UV-Vis Spectroscopy and Kubelka-Munk function, its value being 2.45 eV. A detailed study of the electronic properties has also been carried out using the density functional theory (DFT) techniques impleme…
We report on atomic ordering of B-site transition-metals and magnetic properties of epitaxial La2CrFeO6 double-perovskite films grown by pulsed-laser deposition under various conditions. The highest ordered sample exhibited a fraction of antisite-disorder of only 0.05 and a saturation magnetization of ~2μ_{B} per formula unit at 5 K. The result is consistent with the antiferromagnetic ordering of local spin moment (3d^{3}_{\downarrow}3d^{5}_{\uparrow}; S = -3/2+5/2 = 1). Therefore, the magnetic ground state of La2CrFeO6 double-perovskite that has been long debate is unambiguously revealed to b…
Lead-free double perovskite halides are emerging optoelectronic materials that are alternatives to lead-based perovskite halides. Recently, single-crystalline double perovskite halides were synthesized, and their intriguing functional properties were demonstrated. Despite such pioneering works, lead-free double perovskite halides with better crystallinity are still in demand for applications to novel optoelectronic devices. Here, we realized highly crystalline Cs2AgBiBr6 single crystals with a well-defined atomic ordering on the microscopic scale. We avoided the formation of Ag vacancies and t…
The vacancy-ordered double perovskites (VODP) are emerging materials for the renewable energy because of their extraordinary stability. In the present work, we have addressed the structural, electronic and optical properties of the A$_2$TiX$_6$ (A= Cs or NH$_4$ and X= Cl or Br) organic/inorganic halide VODPs based on first-principles calculations. Our results demonstrate that these compounds have several interesting properties, including high stability, suitable band gap and excellent optical absorption. The band structure calculations for the Cs$_2$TiBr$_6$ and (NH$_4$)$_2$TiBr$_6$ perovskite…
We have developed a multi-scale model for organic-inorganic hybrid perovskites (HPs) that applies quantum mechanical (QM) calculations of small HP supercell models to large coarse-grained structures. With a mixed quantum-classical hopping model, we have studied the effects of cation disorder on charge mobilities in HPs, which is a key feature to optimize their photovoltaic performance. Our multi-scale model parametrizes the interaction between neighboring methylammonium cations (MA$^+$) in the prototypical HP material, methylammonium lead triiodide (CH$_3$NH$_3$PbI$_3$, or MAPbI$_3$). For the …
Tunability of the partially ordered double perovskite (PODP) and coexisting spin-glass phase in SrMn1-xWxO3 (x=0.20 to 0.40) have been studied using neutron powder diffraction (NPD), muon spin relaxation (MuSR), and magnetic susceptibility (X) measurements. Structural studies reveal that SrMn1-xWxO3 undergoes a quasi-continuous transformation from simple perovskite (Pm-3m) to PODP (P21/n) phase as x increases. Xdc(T) and Xac(T) measurements show a sharp cusp-like peak at a spin glass transition, Tg. The muon relaxation rate (λ) peaks at Tg following a critical growth, given by λ=λ(0).t-w [t=(T…
Magnetic structures and the relationship between spin and charge-orbital orderings of an A-site ordered double-perovskite manganite SmBaMn2O6, an anticipated multiferroic material, were investigated by means of neutron diffraction. The spin arrangement in MnO2 planes perpendicular to the c axis is revealed to be the same as that in the A-site disordered half-doped manganites CE-type but the stacking pattern is found to be different displaying a unique twofold period. The temperature dependence of the superlattice magnetic and nuclear reflections clarifies that the antiferromagnetic spin orderi…
We have measured high-field magnetization and magnetoresistance of polycrystalline samples of the A-site ordered perovskite CaCu3Ti4-xRuxO12 (x=0 - 4) utilizing a non-destructive pulsed magnet. We find that the magnetization for x=0.5, 1.0 and 1.5 is nonlinear, and tends to saturate in high fields. This is highly nontrivial because the magnetization for x=0 and 4 is linear in external field up to the highest one. We have analyzed this field dependence based on the thermodynamics of magnetic materials, and propose that the external fields delocalize the holes on the Cu2+ ions in order to maximi…
By means of synchrotron x-ray and electron diffraction, we studied the structural changes at the charge order transition $T_{CO}$=176 K in the mixed-valence quadruple perovskite (NaMn$_3$)Mn$_4$O$_{12}$. Below $T_{CO}$ we find satellite peaks indicating a commensurate structural modulation with the same propagation vector q =(1/2,0,-1/2) of the CE magnetic order that appears at low temperature, similarly to the case of simple perovskites like La$_{0.5}$Ca$_{0.5}$MnO$_3$. In the present case, the modulated structure together with the observation of a large entropy change at $T_{CO}$ gives evide…
Hitting hard on the binary halides yields in the formation of Cs2[AgIn]Br6. The lead-free double perovskite marks, although not usable itself, a further step forward in finding sustainable and durable perovskite materials for photovoltaic applications. Cs2[AgIn]Br6 is one of the prominent examples of double perovskites materials that have been suggested to circumvent the use of lead compounds in perovskite solar cells. We herein report the successful synthesis of the material using a mechanochemical approach. It crystallizes in an elpasolite-type structure, an ordered perovskite superstructure…
Using density functional calculations we explore the properties of as-yet-unsynthesized $3d - 5d$ ordered double perovskites ($A_2BB'$O$_6$) with highly polarizable Bi$^{3+}$ ions on the $A$ site. We find that the Bi$_2$NiReO$_6$ and Bi$_2$MnReO$_6$ compounds are insulating and exhibit a robust net magnetization that persists above room temperature. When the in-plane lattice vectors of the pseudocubic unit cell are constrained to be orthogonal (for example, by coherent heteroepitaxy), the ground states are ferroelectric with large polarization and a very large uniaxial magnetocrystalline aniso…
Shifting the Fermi energy in solids by doping, defect formation or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the ionic limit, such changes are described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In this picture, when the solar absorber CsSnI3 loses 50 % of its Sn atoms thereby forming the ordered vacancy compound Cs2SnI6, the Sn is said to ch…
Switchable Polarization in an A-site Deficient Perovskite through Vacancy and Cation Engineering
Kyoto University（京都大学）；Nantes Université（南特大学）；The University of Tokyo（东京大学）；Japan Fine Ceramics Center（日本先进陶瓷中心）；Kyushu University（九州大学）；Pennsylvania State University（宾夕法尼亚州立大学）
