Strongly coupled electronic, magnetic, and lattice degrees of freedom in LaCo[subscript 5] under pressure
Abstract not provided
Stillwell, Ryan L.↗
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Neutron-scattering-based evidence for interacting magnetic excitons in LaCo O 3
Not Available
El-Khatib, S.↗
Flat band driven itinerant magnetism in the Co-pnictides CaCo 2 As 2 and LaCo 2 P 2
Flat bands can induce strong electron correlation effects that help stabilize both magnetic and superconducting states. Here, in this study, we carry out angle-resolved photoemission spectroscopy and density functional theory calculations to study the electronic structure of the Co-pnictides CaCo 2 As 2 and LaCo 2 P 2 . We find that the 𝑘 𝑧 Fermi topology of ferromagnetic LaCo 2 P 2 is markedly two-dimensional, while the antiferromagnetic CaCo 2 As 2 develops a 3D Fermi surface described by a zigzaglike band dispersion perpendicular to the Co-As plane. Furthermore, the magnetism is driven by the electronic correlations of the flat bands with 𝑑 𝑥𝑦 and 𝑑 𝑧 2 orbital character at the Fermi level. Our results link the electronic dimensionality and the magnetic order and emphasize the critical role of the As-As and P-P bond strength along the 𝑐 direction to understand the electronic band structure and the rich phase diagram of transition metal pnictides.
36 MATERIALS SCIENCE↗
Materials Data on LaCo(BO2)5 by Materials Project
LaCo(BO2)5 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. La3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of La–O bond distances ranging from 2.38–2.95 Å. Co2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Co–O bond distances ranging from 2.08–2.30 Å. There are five inequivalent B3+ sites. In the first B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.37–1.39 Å. In the second B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.36–1.39 Å. In the third B3+ site, B3+ is bonded to four O2- atoms to form corner-sharing BO4 tetrahedra. There are a spread of B–O bond distances ranging from 1.46–1.52 Å. In the fourth B3+ site, B3+ is bonded to four O2- atoms to form corner-sharing BO4 tetrahedra. There are a spread of B–O bond distances ranging from 1.46–1.50 Å. In the fifth B3+ site, B3+ is bonded to four O2- atoms to form corner-sharing BO4 tetrahedra. There are a spread of B–O bond distances ranging from 1.46–1.50 Å. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to one La3+, two equivalent Co2+, and one B3+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one La3+, one Co2+, and two B3+ atoms. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one La3+ and two B3+ atoms. In the fourth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one La3+ and two B3+ atoms. In the fifth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two equivalent La3+ and two B3+ atoms. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Co2+ and two B3+ atoms. In the seventh O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one La3+, one Co2+, and two B3+ atoms. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Co2+ and two B3+ atoms. In the ninth O2- site, O2- is bonded in a bent 120 degrees geometry to one La3+ and two B3+ atoms. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent La3+ and one B3+ atom.
36 MATERIALS SCIENCE↗
Materials Data on LaCO by Materials Project
LaCO crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. La is bonded in a 4-coordinate geometry to three equivalent C and four equivalent O atoms. There are two shorter (2.83 Å) and one longer (2.87 Å) La–C bond lengths. There are two shorter (2.41 Å) and two longer (2.43 Å) La–O bond lengths. C is bonded in a distorted rectangular see-saw-like geometry to three equivalent La and one C atom. The C–C bond length is 1.26 Å. O is bonded to four equivalent La atoms to form a mixture of edge and corner-sharing OLa4 tetrahedra.
36 MATERIALS SCIENCE↗
On the ground and excited electronic states of LaCO and AcCO
MRCI, MRCI+Q, and CCSD(T) calculations were performed to investigate the low-lying states of LaCO and AcCO species and their potential energy curves, geometries, and energy related properties are reported.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Materials Data on LaCo by Materials Project
LaCo1 crystallizes in the cubic I2_13 space group. The structure is three-dimensional. La is bonded in a 8-coordinate geometry to eight equivalent Co atoms. There are a spread of La–Co bond distances ranging from 2.62–3.41 Å. Co is bonded in a 1-coordinate geometry to eight equivalent La and three equivalent Co atoms. All Co–Co bond lengths are 2.96 Å.
36 MATERIALS SCIENCE↗
Unlocking the Potential of A-Site Ca-Doped LaCo 0.2 Fe 0.8 O 3-δ : A Redox-Stable Cathode Material Enabling High Current Density in Direct CO 2 Electrolysis
Massive carbon dioxide (CO 2 ) emission from recent human industrialization has affected the global ecosystem and raised great concern for environmental sustainability. The solid oxide electrolysis cell (SOEC) is a promising energy conversion device capable of efficiently converting CO 2 into valuable chemicals using renewable energy sources. However, Sr-containing cathode materials face the challenge of Sr carbonation during CO 2 electrolysis, which greatly affects the energy conversion efficiency and long-term stability. Thus, A-site Ca-doped La1– x CaxCo 0.2 Fe 0.8 O 3-δ (0.2 ≤ x ≤ 0.6) oxides are developed for direct CO 2 conversion to carbon monoxide (CO) in an intermediate-temperature SOEC (IT-SOEC). With a polarization resistance as low as 0.18 O cm 2 in pure CO 2 atmosphere, a remarkable current density of 2.24 A cm –2 was achieved at 1.5 V with La 0.6 Ca 0.4 Co 0.2 Fe 0.8 O 3-δ (LCCF64) as the cathode in La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3-δ (LSGM) electrolyte (300 µm) supported electrolysis cells using La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) as the air electrode at 800 °C. Furthermore, symmetrical cells with LCCF64 as the electrodes also show promising electrolysis performance of 1.78 A cm –2 at 1.5 V at 800 °C. In addition, stable cell performance has been achieved on direct CO 2 electrolysis at an applied constant current of 0.5 A cm –2 at 800 °C. The easily removable carbonate intermediate produced during direct CO 2 electrolysis makes LCCF64 a promising regenerable cathode. The outstanding electrocatalytic performance of the LCCF64 cathode is ascribed to the highly active and stable metal/perovskite interfaces that resulted from the in situ exsolved Co/CoFe nanoparticles and the additional oxygen vacancies originated from the Ca 2 Fe 2 O 5 phase synergistically providing active sites for CO 2 adsorption and electrolysis. Here this study offers a novel approach to design catalysts with high performance for direct CO 2 electrolysis.
30 DIRECT ENERGY CONVERSION↗
Superconductivity of magnetic Sm-substituted LaCo{sub 2}B{sub 2}
In this work, superconductivity with a maximum superconducting transition onset temperature T{sub C} of 3.6 K is reported in La{sub 1-x}Sm{sub x}Co{sub 2}B{sub 2} in the concentration range 0.12 ≤ x ≤ 0.20. Substitution of magnetic Sm ions with 4f electrons for La is beneficial for superconductivity in the system. The low upper critical field of La{sub 0.8}Sm{sub 0.2}Co{sub 2}B{sub 2} suggests that the dominant magnetic-field suppressing superconducting mechanism is the orbit pair-breaking effect. A special specific-heat anomaly is observed around T{sub C}.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
( LaCo O 3 ) n / ( SrCo O 2.5 ) n superlattices: Tunable ferromagnetic insulator
Ferromagnetic insulators have great potential for spintronic applications. For such applications, it is essential to find materials with a robust and controllable ferromagnetic insulating phase. Yet, because ferromagnetism in functional transition-metal oxides is usually coupled to metallicity, ferromagnetic insulators are very rare and independent control of their magnetic and electrical properties is difficult. In this study, the electrical, magnetic, and optical properties of (LaCoO 3 ) n /(SrCoO 2.5 ) n superlattice films are investigated for the manipulation of the ferromagnetic insulating phase. While the superlattices remain insulating irrespective of the periodicity n, the electronic structure and magnetic state vary drastically. Superlattices with large periodicities n of 10 and 20 show a ferromagnetic transition at a critical temperature T C of ~80K. With decreasing periodicity and increasing interface density of the superlattices, system with n =4 becomes almost nonmagnetic, while in systems with n =2 and 1, a reentrant ferromagnetic phase is observed at T C of ~180 and ~225K, respectively. Optical spectroscopy reveals that the fine control of the magnetic ground state is achieved by the modified electronic structure associated with the spin-state transition. Our findings indicate an important design principle to create and manipulate the ferromagnetic insulating properties of Co-based oxide thin films.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Switchable orbital polarization and magnetization in strained LaCo O 3 films
Strain engineering of epitaxial heterostructures offers opportunities to control the orbital degree of freedom by lifting the degeneracy of e g states. In this work, we show that the orbital occupation in LaCoO 3 (LCO) films can be switched between two degenerate e g bands with epitaxial strain. The orbital polarization of nearly -100% (or 100%) is controlled by depleting occupation of the d x2-y2 (or d( 3z2-r2 ) orbital entirely in LCO for large compressive (or moderate tensile) strain. The change of electronic configuration associated with the spin-state transition modulates the magnetization of strained LCO films. Under compressive strain, LCO films exhibit a small magnetization without long-range ferromagnetic ordering. With tensile-strain increases, the magnetization of LCO films increases and reaches the maximum value when the bonding angle (Co-O-Co) is close to 180° and the in-plane bond length (Co-O) is unstretched. Our results highlight the role of octahedral distortion and spin-state crossover in tailoring the magnetic properties of cobaltite thin films, indicating an attractive route to deliberately control the orbital polarization that can be tuned to maximize the functionality of oxide heterostructures.
36 MATERIALS SCIENCE↗
Strain-induced majority carrier inversion in ferromagnetic epitaxial LaCo O 3 - δ thin films
Tensile-strained LaCoO 3-δ thin films are ferromagnetic, in sharp contrast to the zero-spin bulk, although no clear consensus has emerged as to the origin of this phenomenon. While magnetism has been heavily studied, relatively little attention has been paid to electronic transport, due to the insulating nature of the strain-stabilized ferromagnetic state. Here, structure, magnetism, and transport are studied in epitaxial LaCoO 3-δ films (10–22-nm thick) on various substrates (from 1.4% compressive to 2.5% tensile strain), using synchrotron x-ray diffraction, scanning probe and transmission electron microscopy, magnetometry, polarized neutron reflectometry, resistivity, and Hall effect. High quality, smooth films are obtained, exhibiting superstructures associated with both oxygen vacancy ordering and periodic in-plane ferroelastic domains. Consistent with prior work, ferromagnetism with an approximately 80–85 K Curie temperature is observed under tension; polarized neutron reflectometry confirms a relatively uniform magnetization depth profile, albeit with interfacial dead layer formation. Electrical transport is found to have similar semiconducting nature to bulk, but with reduced resistivity and activation energy. Hall effect measurements, however, reveal a striking inversion of the majority carrier type, from p-type in the bulk and under compression to n-type under tension. While thus far overlooked, ferromagnetism in epitaxial LaCoO 3-δ films is thus directly correlated with n-type behavior, providing important insight into the ferromagnetic state in this system. Here, aided by density functional theory calculations, these results are interpreted in terms of tensile-strain-induced orbital occupation and band structure changes, including a rapid decrease in effective mass at the e g -derived conduction band minimum, and corresponding increase at the valence band maximum.
36 MATERIALS SCIENCE↗
Structure, thermal expansion and electrical conductivity of Nb-substituted LaCoO{sub 3}
The effect of Nb-substitution in LaCoO{sub 3} has been examined by evaluating the electrical conductivity, thermal expansion and crystal structure of the solid solutions LaCo{sub 1-x}Nb{sub x}O{sub 3} (x=0 to 1/3). It was demonstrated that Nb-substitution in LaCoO{sub 3} was mainly compensated by reduction of Co{sup 3+} to Co{sup 2+}, and that oxidation of Co{sup 2+} could destabilise the solid solution. The ambient crystal structure was shown to transform from rhombohedral R3{sup Macron }c perovskite (x=0) to orthorhombic Pbnm (x=0.15, 0.20) and finally to B-site ordered perovskite P2{sub 1}/n (x=0.25, 1/3) perovskite with increasing Nb-substitution. The thermal expansion of LaCo{sub 1-x}Nb{sub x}O{sub 3} was shown to be strongly depressed with increasing Nb-content, and significantly lower thermal expansion was observed for LaCo{sub 2/3}Nb{sub 1/3}O{sub 3} relative to LaCoO{sub 3}. The electrical conductivity was reduced with increasing Nb-content, and semi-conducting properties was demonstrated for LaCo{sub 1-x}Nb{sub x}O{sub 3} in contrast to the metallic behaviour of pure LaCoO{sub 3} at elevated temperature. The thermal expansion, electrical conductivity and the stability of the materials were discussed with emphasis on Co/Nb ordering, the oxidation state and spin transitions of Co. - Graphical abstract: Substitution of Nb in LaCoO{sub 3} increases the unit cell volume, reduces the symmetry of the unit cell and introduces cation ordering. The chemical substitution leads to suppression of the electronic conductivity and reduces the thermal expansion of the lattice. Highlights: Black-Right-Pointing-Pointer Cation ordering and crystal structure is reported for LaCo{sub x}Nb{sub 1-x}O{sub 3}. Black-Right-Pointing-Pointer Substitution of Nb in LaCoO{sub 3} is compensated by reduction of Co{sup 3+} to Co{sup 2+}. Black-Right-Pointing-Pointer Thermal expansion of LaCoO{sub 3} is reduced by Nb-substitution. Black-Right-Pointing-Pointer Electrical conductivity of LaCoO{sub 3} is reduced by Nb-substitution.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermal properties of Ni-substituted LaCoO{sub 3} perovskite
With the objective of exploring the unknown thermodynamic behavior of LaCo{sub 1−x}Ni{sub x}O{sub 3} family, we present here an investigation of the temperature-dependent (10K ≤ T ≤ 300K) thermodynamic properties of LaCo{sub 1−x}Ni{sub x}O{sub 3} (x=0.1, 0.3, 0.5). The specific heat of LaCoO3 with Ni doping in the perovskite structure at B-site has been studied by means of a Modified Rigid Ion Model (MRIM). This replacement introduces large cation variance at B-site hence the specific heat increases appreciably. We report here probably for the first time the cohesive energy, Reststrahlen frequency (υ) and Debye temperature (θ{sub D}) of LaCo{sub 1−x}Ni{sub x}O{sub 3} compounds.
36 MATERIALS SCIENCE↗
New tetragonal derivatives of cubic NaZn{sub 13}-type structure: RNi{sub 6}Si{sub 6} compounds, crystal structure and magnetic ordering (R=Y, La, Ce, Sm, Gd–Yb)
Novel RNi{sub 6}Si{sub 6} compounds adopt the new CeNi{sub 6}Si{sub 6}-type structure for R=La–Ce (tP52, space group P4/nbm N 125-1) and new YNi{sub 6}Si{sub 6}-type structure for R=Y, Sm, Gd–Yb (tP52, space group P4{sup ¯}b2N 117) that are tetragonal derivative of NaZn{sub 13}-type structure, like LaCo{sub 9}Si{sub 4}-type. The CeNi{sub 6}Si{sub 6}, GdNi{sub 6}Si{sub 6}, TbNi{sub 6}Si{sub 6}, DyNi{sub 6}Si{sub 6} and HoNi{sub 6}Si{sub 6} compounds are Curie–Weiss paramagnets down to ∼30 K, and do not order magnetically down to 5 K. However, the inverse paramagnetic susceptibility of LaNi{sub 6}Si{sub 6} does not follow Curie–Weiss law. The DyNi{sub 6}Si{sub 6} shows ferromagnetic-like saturation behaviour at 5 K in applied fields of 50 kOe, giving rise to a magnetic moment value of 6.5 μ{sub B}/f.u. in 50 kOe. The powder neutron diffraction study in zero applied filed indicates square modulated the c-collinear antiferromagnetic ordering of TbNi{sub 6}Si{sub 6} with K=[±1/4, ±1/4, 0] wave vector below ∼10 K. - Graphical abstract: Novel (La, Ce)Ni{sub 6}Si{sub 6} compounds adopt the new CeNi{sub 6}Si{sub 6}-type structure and (Y, Sm, Gd–Yb) adopt the new YNi{sub 6}Si{sub 6}-type structure that are tetragonal derivative of NaZn{sub 13}-type structure, like LaCo{sub 9}Si{sub 4}-type. The CeNi{sub 6}Si{sub 6}, GdNi{sub 6}Si{sub 6}, TbNi{sub 6}Si{sub 6}, DyNi{sub 6}Si{sub 6} and HoNi{sub 6}Si{sub 6} compounds are Curie–Weiss paramagnets down to ∼30 K, and do not order magnetically down to 4.2 K. The powder neutron diffraction study in zero applied filed indicates square modulated the c-collinear antiferromagnetic ordering of TbNi{sub 6}Si{sub 6} with K=[±1/4, ±1/4, 0] wave vector below ∼10 K. Display Omitted - Highlights: • The new (La, Ce)Ni{sub 6}Si{sub 6} compounds adopt the new CeNi{sub 6}Si{sub 6}-type structure. • The new (Y, Sm, Gd–Yb)Ni{sub 6}Si{sub 6} compounds adopt the new YNi{sub 6}Si{sub 6}-type structure. • TbNi{sub 6}Si{sub 6} has square modulated c-collinear antiferromagnetic ordering below ∼10 K.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Material properties of perovskites in the quasi-ternary system LaFeO{sub 3}–LaCoO{sub 3}–LaNiO{sub 3}
An overview is presented on the variation of electrical conductivity, oxygen permeation, and thermal expansion coefficient as a function of the composition of perovskites in the quasi-ternary system LaFeO{sub 3}–LaCoO{sub 3}–LaNiO{sub 3}. Powders of thirteen nominal perovskite compositions were synthesized under identical conditions by the Pechini method. The powder X-ray diffraction data of two series, namely La(Ni{sub 0.5}Fe{sub 0.5}){sub 1−x}Co{sub x}O{sub 3} and LaNi{sub 0.5-x}Fe{sub x}Co{sub 0.5}O{sub 3}, are presented after the powders had been sintered at 1100 °C for 6 h in air. The measurements revealed a rhombohedral structure for all compositions except LaNi{sub 0.5}Fe{sub 0.5}O{sub 3} for which 60% rhombohedral and 40% orthorhombic phase was found. The maximum DC electrical conductivity value of the perovskites at 800 °C was 1229 S cm{sup −1} for the composition LaCoO{sub 3} and the minimum was 91 S cm{sup −1} for the composition LaCo{sub 0.5}Fe{sub 0.5}O{sub 3}. The oxygen permeation of samples with promising conductivities at 800 °C was one order of magnitude lower than that of La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3} (LSCF). The highest value of 0.017 ml cm{sup −2} min{sup −1} at 950 °C was obtained with LaNi{sub 0.5}Co{sub 0.5}O{sub 3}. The coefficients of thermal expansion varied in the range of 13.2×10{sup −6} K{sup −1} and 21.9×10{sup −6} K{sup −1} for LaNi{sub 0.5}Fe{sub 0.5}O{sub 3} and LaCoO{sub 3}, respectively. {sup 57}Fe Mössbauer spectroscopy was used as probe for the oxidation states, local environment and magnetic properties of iron ions as a function of chemical composition. The substitution had a great influence on the chemical properties of the materials. - Graphical abstract: Compositional dependence of isothermal electrical conductivity at 800 °C and thermal expansion coefficient in the series La(Fe{sub 0.5}Ni{sub 0.5}){sub (1−x)}Co{sub x}O{sub 3} and LaNi{sub 0.5−x}Fe{sub x}Co{sub 0.5}O{sub 3}.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
La-Based Perovskite Oxide Catalysts for Alkaline Oxygen Reduction: The Importance of Electrochemical Stability
Alkaline fuel cells represent a promising energy conversion technology since they enable the use of precious metal-free electrocatalysts for the oxygen reduction reaction. Among these, La-based perovskite oxides, with great compositional and structural tunability, are especially attractive. However, we believe that the current literature lacks a thorough understanding of their inherent (in)stability issues. Here, in this study, we report on nine La-based perovskite oxide electrocatalysts for the oxygen reduction reaction, including LaMO 3 (M = Mn, Co, Ni) and LaCo x M 1–x O 3 (M = Mn, Ni; x = 0.9, 0.5, 0.1). While some exhibited initial promising activity, they all degraded significantly, even after brief electrochemical testing. Through comprehensive structural characterization of LaCo 0.9 Mn 0.1 O 3 , particularly scanning transmission electron microscopy, we found evidence to support a degradation mechanism in which the B-site cation species irreversibly leach from the perovskite under testing conditions. A sample cycled 10 000 times from +0.4 to +1.2 V vs reversible hydrogen electrode (RHE) showed an amorphous La oxide shell 1–2 nm thick. Bulk analyses showed that B-site leaching also occurs for samples soaked in 1 M KOH or pure EtOH. The mechanistic insights provided here should help inform the future design of La-based perovskite oxide electrocatalysts for alkaline fuel cells and stress the importance of stability metrics validating claims of promising electrocatalytic activity.
Seok, Jeesoo↗