Nature of magnetism in Ca3Co2O6

We find using local spin density approximation + Hubbard U band structure calculations that the novel one-dimensional cobaltate Ca3Co2O6 is not a ferromagnetic half-metal but a Mott insulator. Both the octahedral and the trigonal Co ions are formally trivalent, with the octahedral being in the low-spin and the trigonal in the high-spin state. The inclusion of the spin-orbit coupling leads to the occupation of the minority-spin d2 orbital for the unusually coordinated trigonal Co, producing a giant orbital moment (1.57 microB). It also results in an anomalously large magnetocrystalline anisotropy (of order 70 meV), elucidating why the magnetism is highly Ising-like. The role of the oxygen holes, carrying an induced magnetic moment of 0.13 microB per oxygen, for the exchange interactions is discussed.     

Slow magnetic order-order transition in the spin chain antiferromagnet Ca3Co2O6

Using powder neutron diffraction, we have discovered an unusual magnetic order-order transition in the Ising spin chain compound Ca3Co2O6. On lowering the temperature, an antiferromagnetic phase with a propagation vector k=(0.5,-0.5,1) emerges from a higher temperature spin density wave structure with k=(0,0,1.01). This transition occurs over an unprecedented time scale of several hours and is never complete.     

Reduced magnetic disorder at low temperature in Ca3Co2O6 via zinc substitution

ABSTRACT

The compound Ca₃Co₂O₆ undergoes a transition into a spin-density wave (SDW) state near 24?K. Below ～10?K, this unstable SDW state coexists with a nearly- degenerate commensurate antiferromagnetic state as well as short-range magnetic order. Clear signatures of this strong magnetic disorder have been observed in the response of entropy to changing magnetic field and temperature. We performed a calorimetry study of Ca₃Co₂O₆ and Ca₃Co_1.9Zn_0.1O₆ in order to compare their entropic responses at low temperature. Our results for Ca₃Co₂O₆ reveal that ΔS(T, H)?≡?S(T, H)?S(T, H?=?0) increases as either temperature or magnetic field increase. In contrast, ΔS data for Ca₃Co_1.9Zn_0.1O₆ were relatively unresponsive to changes in temperature or field, suggesting that Zn substitution may reduce the low-temperature magnetic disorder observed in Ca₃Co₂O₆. These results are discussed within the context of two cases (Ca₃Co₂O₆ under applied pressure and Ca_2.75R_0.25Co₂O₆ (R?=?Dy, Lu)) in which a single magnetic ground state is stabilised.     

Tailor-made electronic and magnetic properties in one-dimensional pure and Y-substituted Ca3Co2O6

Full-potential density-functional calculations show that the electronic structure of one-dimensional ferrimagnetic Ca3Co2O6 varies from metal to half metal to insulator as its magnetic ordering changes from the ferrimagnetic through the ferromagnetic to the paramagnetic state. The present Letter is the first to establish the occurrence of half metallicity in one-dimensional oxides. Moreover, the electronic and magnetic properties of this material can be tuned by substitution of Y for Ca, as shown by our detailed study on Ca(3-x)YxCo2O6 (x = 0, 0.3, 0.75, and 1). The Co ions are in two different valence states [Co4+ (low-spin) and Co2+ (high-spin)], and hence the occurrence of charge ordering in addition to spin ordering is established. For specific Y concentrations we predict a rarely seen combination of ferromagnetic and insulating behavior.     

Ca3Co2O6及其掺镍体系的电子结构计算

用离散变分密度泛函方法(DFT-DVM)计算了钴酸盐Ca3Co2O6及其掺镍体系,讨论了电子结构,化学键等与热电性能之间的关系．结果表明,价带和导带主要由Co3d,Ni3d和O2p原子轨道贡献．价带和导带之间的能隙宽度表现出了半导体电子结构特征,且掺镍体系的能隙比不掺镍体系窄．掺镍体系的共价键和离子键都比不掺镍体系弱．由此得到,掺镍后体系的热电性能将有所改善．     

Steplike magnetization in a spin-chain system:Ca3Co2O6

Because of a ferromagnetic in-chain coupling between Co3+ ions at trigonal sites, Co2O6 chains are considered as large rigid spin moments. The antiferromagnetic Ising model on the triangular lattice is applied to describe an interchain ordering. An evolution of metastable states in a sweeping magnetic field is investigated by the single-flip technique. At the first approximation two steps in the magnetization curve and a plateau at 1/3 of the saturation magnetization are found. Four steps in magnetization are determined in high-order approximations in agreement with experimental results.     

Thickness-dependent optical band gap in one-dimensional Ca3Co2O6 nanometric films

Recent studies on the physical properties of Ca₃Co₂O₆ nanometric samples have shown that their properties are significantly different from those of the bulk samples. The origin of this change is not trivial. We have carried out optical measurements on Ca₃Co₂O₆ thin films with different thicknesses in order to characterize their electronic structure using optical spectroscopy measurements. The absorption spectra show a dependence on the film thickness that is correlated to the grain size in the polycrystalline layers. We found that the optical band gap increases from 1.3 to 1.55 eV when the thickness changes from 35 to 100 nm. The change in the band gap evolution with the film thickness is discussed in terms of both the amorphous effect and the grain size in the Ca₃Co₂O₆ thin films. Finally, we show that these results are consistent with recent measurements concerning magnetic and electrical properties of Ca₃Co₂O₆ nanometric samples.     

Negative chemical pressure effects induced by Y substitution for Ca on the ‘exotic’ magnetic behavior of the spin-chain compound, Ca3Co2O6

The magnetic behavior of a solid solution, Ca_{3 x} Y_x CO₂ O₆, based on the ‘exotic’ spin-chain compound, Ca₃Co₂O₆, crystallizing in K₄CdCl₆-derived rhombohedral structure is investigated. Among the compositions investigated(x = 0.0, 0.3, 0.5, 0.75 and 1.0), single-phase formation persists up tox = 0.75, with the elongation of the c-axis. The present investigations reveal that the temperature at which the ‘so-called’ ‘partially disordered antiferromagnetic structure’ sets in (which occurs at 24 K for the parent compound,x = 0.0) undergoes gradual reduction with the substitution of Y for Ca, attaining the value of about 2.2 K for the nominalx = 1.0. The trend observed in this characteristic temperature is opposite to that reported under external pressure, thereby establishing that Y substitution exerts negative chemical pressure. Anomalous steps observed in the isothermal magnetization at very low temperatures (around 2 K) forx = 0.0, which have been proposed to arise from ‘quantum tunneling effects’ are found to vanish by a small substitution (x = 0.3) of Y for Ca. Systematics in AC and DC magnetic susceptibility behavior with Y substitution for Ca have also been probed. We believe that the present results involving the expansion of chain length without disrupting the magnetic chain may be useful to the overall understanding of the novel magnetism of the parent compound.     

Thermal conductivity and magnetic properties of the B substituted Ca3Co4O9

In this study, we reported the effects of the boron (B) substitution into the Ca site in the Ca₃Co₄O₉ system on the electrical, thermal and magnetic properties between 300 K and 5 K. The results indicated that the B-substitution into the system caused an increase of resistivity due to the decrease on carrier concentration. Thermal conductivity decreased for the x = 0.5 B-substituted sample and then increased with increasing the B-content. Analysis on the thermal conductivity of samples showed that the phonon–phonon interaction term is the dominant component in the total thermal conductivity for all the samples. It was found that the point defect contribution to the thermal conductivity increased by increasing the B-content. The temperature dependence of magnetic susceptibility showed a paramagnetic behavior at room temperature and ferrimagnetic behavior below 20 K for unsubstituted sample. But, the magnetization decreased in the B-substituted samples. The substitution of B into the Ca site destroyed the interlayer coupling, which resulted in the decrease of the ferromagnetic behavior. The susceptibility data was fitted using Curie–Weiss law with temperature independent term and the μ_eff values were calculated to be 1.42 μ_B and 3.89 μ_B for unsubstituted sample and the highest B-substitution, respectively.     

Field-induced orbital and magnetic phases in Ca3Ru2O7

Magnetic-field- and temperature-dependent Raman scattering studies of Ca3Ru2O7 reveal dramatic field-dependent properties arising from transitions between various complex orbital and magnetic phases, including a field-induced orbital-ordered to orbital-disordered transition (H(o) // hard axis), and a reentrant orbital-ordered to orbital-disordered to orbital-ordered transition (H(o) // easy axis). We find that the dramatic magnetic-field properties are most prevalent in a "mixed"-magnetic and -orbital phase regime, providing evidence for a strong connection between orbital phase inhomogeneity and "colossal" field effects in the ruthenates.     

Superconductivity and magnetic order in CaLaBaCu3O z

X-ray diffraction, thermogravimetric analysis, magnetization and Mossbauer studies of a⁵⁷Fe probe, in CaLaBa(Cu_1−x Fe _x )₃O _z withz=7, 6.5 andx=0.00 to 0.05 have been performed. Forz=7,T _c drops from 74 K forx=0.00 to 35 K forx=0.05. In CaLaBa(Cu_1−x Fe _x )₃O _z withz=7, 10% of the iron is magnetically ordered withH _eff=530 K kOe andT _N=400 K, even though the sample is superconducting. In the oxygen poor, non-superconducting samples (z=6.5) 20% of the iron is magnetically ordered withH _eff=340 kOe andT _N=340 K. Since the iron reflects the magnetic order of the Cu(2) ions, this may show that perhaps two inequivalent Cu(2) sites exist in CaLaBa(Cu_1−x Fe _x )₃O₇, ones of which is magnetically ordered. The experimental observations may be interpreted in terms of the special crystal structure which can allow superconductivity and magnetism to coexist, probably in separate Cu(2) planes.     

First order magnetic phase transition in GeCo2O4

The antiferromagnetic compound GeCo₂O₄ exhibits a magnetic phase transition characterized by thermal hysteresis of the susceptibility versus temperature curve and by a diffuse neutron scattering with a small correlation length. The data are compared to the expected first-order phase transition of the n ≥ 4 component vector models.     

The magnetic hyperfine interaction of111Cd in the spinels Fe3O4 and Co3O4

The perturbed angular correlation (PAC) method was applied to study the temperature dependence of the magnetic hyperfine fields in¹¹¹In-doped polycrystalline Fe₃O₄ and Co₃O₄. The critical behaviour near the magnetic phase transitions has been investigated. The changes occuring near the Vervey transition in Fe₃O₄ and the path of the supertransferred magnetic fied in Co₃O₄ are discussed. The results are compared with results obtained from Mössbauer spectroscopy.     

Crystal structure and magnetization of a Co3B2O6 single crystal

The crystal structure and magnetic properties of Co₃B₂O₆ single crystals are studied. Orthorhombic symmetry with space group Pnnm is detected at room temperature. The measurements of static magnetization and dynamic magnetic susceptibility reveal two magnetic anomalies at T ₁ = 33 K and T ₂ = 10 K and an easy-axis magnetic anisotropy. The effective magnetic moment indicates a high-spin state of the Co²⁺ ion. A spin-flop transition is found at low temperatures and H _sf = 23 kOe. EXAFS spectra of the K-edge absorption of Co are recorded at various temperatures, the temperature-induced changes in the parameters of the local environment of cobalt are analyzed, and the effective Co-Co and Co-O distances are determined. The magnetic interactions in the crystal are analyzed in terms of an indirect coupling model.