The magnetism of Zn-doped colossal magnetoresistance materials Fe1−xZnxCr2S4 (0⩽x⩽1)

The polycrystalline samples of Zn-doped Fe_1−xZn_xCr₂S₄ (0⩽x⩽1) were prepared by the conventional solid-state synthesis method. The magnetic homogeneity has been proved by the measurements of the alternating current (AC) magnetic susceptibility. We presented a detailed study of Zn-doping effect on the magnetism. It is found that the magnetism does not change monotonically with substituting nonmagnetic Zn²⁺ ions for Fe²⁺ ions. The difference between the magnetic moments for the samples with respective doping level can be ascribed to the variation of compensation between the Fe²⁺ and Cr³⁺ sublattices as the Fe²⁺ concentration is varied. The Zn-doping leads to spin reversal of Cr³⁺ ions. Based on the spin orientation of Fe²⁺ and Cr³⁺ ions in FeCr₂S₄ and ZnCr₂S₄ at 0 K, we suggest a phenomenological model describing the magnetism and the doping level dependence of the up-spin proportion of Cr³⁺ ions. The up-spin proportion of Cr³⁺ ions, denoted by y, as a function of doping level in zero fields is linear. However, y in magnetic fields cannot be fitted linearly, which shows a maximum. The above results can be described qualitatively by the effect of the applied magnetic field on the AB, AA, and BB interactions of the spinels with the formula ABS₄.     

On the n-p phase transitions in Mn1-x Cu x Cr2S4

The Seebeck coefficient for polycrystalline samples of: 1. Mn_1-x Cu _x Cr₂S₄ (0.0 ≤ x < 1.00) at 313 K and 2. MnCr₂S₄ between 313–393 K is presented. The electrical resistivity of Mn_1-x Cu _x Cr₂S₄ as a function of x at the room temperature is also presented. The n-p phase transition is observed in two cases: 1. on changing x at constant temperature (313 K) for 0.0 ≤ x ≤ 0.1 and 2. on changing temperature for MnCr₂S₄ at about 326 K. The first case is probably connected with the noncollinear ferromagnetic interaction of the chromium 3+ and 4+ ions. The second case follows from the strong ferrimagnetic interaction of the Mn²⁺ and Cr³⁺ ions in pure MnCr₂S₄.     

Electron hopping in Fe1−xCuxCr2S4 (0<x<0.5)

A theoretical expression for the line shape of the Mössbauer spectra in the presence of electron hopping between Fe²⁺ and Fe³⁺ is obtained by using a simple stochastic model. Analyses based upon this expression show that the origin of the complicated Mössbauer spectra observed in the magnetic semiconductors Fe_1?xCu_xCr₂S₄ (0<x<0.5) at 77 K is electron hopping between Fe⁺² and Fe³⁺ This hopping occurs at a rate of a few MHz. Quantitative estimates are given for some parameters; the isomer shifts, the internal magnetic fields, the quadrupole splittings and the proportions of Fe²⁺ and Fe³⁺. The valence distribution in this system is determined from the results. For example, the distribution Fe²⁺_0.69Fe³+_0.29Cu¹⁺_0.02Cr³⁺_1.72Cr²⁺_0.28S^2?₄ is obtained for x = 0.02. The existence of Cr²⁺ is concluded.     

Magnetic behavior in the incommensurate phase ∼LaCrS3:: effect of the partial substitution of Cr by Ti on the magnetic properties

Dilution of the magnetic interactions between Cr³⁺ ions by Ti³⁺ ions was observed in the CrS₂ layer of the misfit-layer compound ∼LaCrS₃. Pure ∼LaCrS₃ has complex magnetic properties which are reminiscent of spin glass behavior. This magnetic behavior comes from both the modulated character of the structure and the magnetic frustration of the planar-antiferromagnetic-triangular network of Cr³⁺ ions. Thus, there is a large hysteresis between the zero field cooled and the field cooled magnetic susceptibility curves below the transition temperature (≈75 K). Formation of a solid solution ∼LaCr_1−xTi_xS₃ by the addition of Ti³⁺ ions results in the decrease of transition temperature up to a doping level of x≈0.5, where the transition is no longer observed. The magnetic behavior of the phase with x≈0.5 is similar to that of several random exchange antiferromagnetic compounds.     

Phase transitions and colossal magnetoresistance in CuVxCr1−x S2 layered disulfides

New substances CuV_xCr_1?x S₂ are synthesized in which colossal magnetoresistance (T _C = 95 K, δ_H = ?60%, H = 7 kOe), as well as the sequence of phase transitions with change in the conduction type and magnetic order, is observed as temperature is varied. The change found in the magnetic and electric properties of the CuV_xCr_1?x S₂ compounds may be a consequence of a specific disintegration into Cu⁺Cr³⁺S₂ and Cu²⁺Cr²⁺S₂ and a change in the concentration relation between these electronic phases in the substance bulk.     

Magnetic Phase Transitions in Substituted Spinels of Zn1−x Cu χ Cr2 Se4; 0.0 ≤ x ≤ 0.3

Magnetic and crystallographic properties have been studied by neutron powder diffraction and measurements of magnetization and magnetization hysteresis-loops for substituted spinels of Zn_1?xCu_xCr₂Se₄ with 0.0≤x≤0.3. It is found that the Zn_0.85Cu_0.15Cr₂Se₄ spinel has two magnetic phase transitions at 23.0 K (Néel temperature; T _N) and 410 K (Curie temperature; T _C) and that the Zn_0.70Cu_0.30Cr₂Se₄ spinel has magnetic transitions at 24.5 K (T _N) and 415 K (T _C) on heating. The low-temperature magnetic phase transition is from a spiral antiferromagnet to a ferromagnet, and the high-temperature magnetic phase transition is from a ferromagnet to a paramagnet, while ZnCr₂Se₄ shows a magnetic phase transition only from a spiral antiferromagnet to a paramagnet at about 21.0 K. From neutron powder diffraction, it is also found that the spinels of Zn_1?x Cu _x Cr₂Se₄; 0.0 ≤ x ≤ 0.3. show satellite-like magnetic reflection having indexes (h ± Q, k, l) with Q = 0.470 below T _N and short-range order of spins (spin glass-like) above T _N. The incommensurate antiferromagnetic phase below T _N results from a spiral long-range order of the spins of Cr³⁺. The intermediate ferromagnetic phase between T _N and T _C is related not to the spiral spin order but to double-exchange magnetic interaction among Cr³⁺ and Cr⁴⁺ mediated by current carriers, positive holes, which is made by the substitution of Zn²⁺ ions with Cu¹⁺ ions in Zn_1?x Cu _x Cr₂Se₄.     

Temperature dependent Mössbauer and neutron diffraction studies of Cu x Fe1−x Cr2S4 compounds

The cation distribution and magnetic structure of Cu _x Fe_1?x Cr₂S₄ (x?=?0.1, 0.2, 0.3, 0.4, and 0.5) has been studied by X-ray and neutron diffraction, vibrating sample magnetometer (VSM), and Mössbauer spectroscopy. The charge state of Fe is found to be ferrous (Fe²⁺) for the x?=?0.1 sample; ferric (Fe³⁺) for the x?=?0.5 sample; mixed state (Fe²⁺, Fe³⁺) for the x?=?0.2, 0.3, and 0.4 samples. The Mössbauer spectra of the x?=?0.1 sample show asymmetric line broadening, which is considered to be due to the Jahn–Teller effect of Cu²⁺ ions, and a symmetrical six-line pattern is shown for the x?=?0.5 sample. The valence state of the Cu ions for the x?=?0.1 and 0.5 samples is found to be divalent and monovalent, respectively. The magnetic structure of the samples was determined to be a ferrimagnetic structure with antiparallel alignment of the Fe and Cr ion magnetic moments.     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

Ti1－xCrxO2±δ体系的相关系、晶体结构和磁性能研究

采用溶胶凝胶法制备了Ti_1-xCr_xO_2±δ体系系列样品.利用扫描电子显微镜(SEM)，X射线光电子能谱(XPS)，粉末X射线衍射分析(XRD)方法研究了Ti_1-xCr_xO_2±δ系列样品的颗粒尺寸、形貌、组分化学态、相关系和固溶区范围；并利用超导量子干涉磁强计对样品的磁性能进行了研究.采用Rietveld结构精修的方法研究了Cr的不同掺杂量对TiO₂晶体结构的影响，研究表明，1000℃烧结的样品的固溶区范围是x=0—0.03，为金红石单相；随着Cr掺杂量的增加，金红石相晶胞参数规律性地减小；当x>0.03，为金红石相和CrO₂相两相共存.综合XRD和磁性测量结果，500℃烧结的样品的固溶区范围是x=0—0.02，为锐钛矿单相；随着Cr掺杂量的增加，锐钛矿相晶胞参数规律性地减小；当x≥0.04，为锐钛矿相和绿铬矿相(Cr₂O₃)两相共存.XPS实验结果表明，500℃和1000℃退火的样品中Cr都是以Cr⁺³和Cr⁺⁶两种化学态存在，1000℃烧结的样品中可能有更多的Cr³⁺转化为Cr⁶⁺.根据M-H和M-T曲线的测试结果发现，本文500℃烧结的Ti_1-xCr_xO_2±δ体系样品当x=0—0.02时，为室温铁磁性.当x≥0.04时，由铁磁相和顺磁相所组成，在低温下有较强的铁磁性；室温下主要是顺磁相，铁磁相只占据很小的体积分数. 关键词： 1-xCr_xO_2±δ体系')" href="#">Ti_1-xCr_xO_2±δ体系 相关系 固溶区 磁性能     

Lattice dynamics of ZnSe x S1 − x semiconductor crystals

Recently ultrabroadband infrared solid state lasers based on a new vibronic material Cr²⁺:ZnSe _x S_1–x were demonstrated [1–3]. Cr²⁺ ion substitutes the metal ion (tetrahedral sites), the crystal field of the solid solution is responsible for large inhomogeneous broadening of Cr²⁺ electron states. The crystal field can be reconstructed by investigation of lattice dynamics — optical phonon parameters and dielectric function in IR. We paid special attention to investigation of vibrational and infrared spectroscopic properties of ZnSe _x S_{1 ? x} crystals. A very interesting and somewhat unexpected result of these studies was the existence in the crystals of effective S-Se dipoles, which generate an additional deep dynamically charged level in the forbidden gap of the semiconductors. The results of the first-principles calculations of both the phonon structure and the electron localization in ZnSe _x S_1–x crystals as well as acceptor levels in Cr²⁺: ZnSe crystal are discussed.     

Al-doping effect on the structural and physical properties of delafossite-type oxide CuCrO2

The structure, Raman spectroscopy, magnetization, and dielectric properties of delafossite-type oxide CuCr_1−xAl_xO₂ have been characterized. It was found that Al substitution generates an anisotropic effect on the structure, besides magnetic dilution. The temperature dependence of all samples exhibits paramagnetic behavior at high temperature. Above x=0.2 the ferromagnetic transition at 120 K disappears. It is argued that Al substitution destabilizes the antiferromagnetic order of Cr³⁺ ions and modulates the spin configuration, leading to a weak ferromagnetism. The coupling between the magnetic order and ferroelectric order is also characterized.     

Neutron diffraction and Mössbauer study on FeGa x Cr2−x S4

Ga doped sulphur spinel FeGa _x Cr_2?x S₄ (x = 0.1 and 0.3) have been studied with X-ray, neutron diffraction, and Mössbauer spectroscopy. Rietveld refinement of X-ray, neutron diffraction, and Mössbauer spectroscopy lead to the conclusion that the samples are in inverse spinel type, where most Ga ions are present at octahedral site (B). The neutron diffractions on FeGa _x Cr_2?x S₄ (x = 0.1) above 10 K show long range interaction behaviors and reveal a ferrimagnetic ordering, with the magnetic moment of Fe²⁺(?3.45 μ_B) aligned antiparallel to Cr³⁺ (+2.89 μ_B) at 10 K. Fe ions migrate from the tetrahedral (A) site to the octahedral (B) site with an increase in Ga substitutions. The electric quadrupole splittings of the A and B sites in Mössbauer spectra give direct evidence that Ga ions stimulate an asymmetric charge distribution of Fe ions in the A site.     

Magnetotransport and magnetic properties of sulfospinels Zn x Fe1−x Cr2S4

Cr-based chalcogenide spinels, which do not have heterovalency and distortion-induced ions such as manganese oxides with perovskite structure, have demonstrated the existence of colossal magnetoresistance. In order to investigate the magnetotransport phenomena and magnetic properties of sulfospinels Zn _x Fe_1?x Cr₂S₄, polycrystalline Zn _x Fe_1?x Cr₂S₄ samples were synthesized in the 0?≤?x?≤?0.2 range by a solid reaction method. The crystal structure for x?=?0.05, 0.1, and 0.2 turned out to be cubic at room temperature by X-ray diffraction measurement. In magnetoresistance measurement, Zn _x Fe_1?x Cr₂S₄ samples indicate that this system is semiconducting below about 150 K. The temperature of maximum magnetoresistance is almost consistent with Curie temperature. The isomer shift and the electric quadrupole shift of Zn _x Fe_1?x Cr₂S₄ samples by Mössbauer experiment show that Fe²⁺ ions occupy the tetrahedral site in the spinel structure. As the Zn ions are substituted for Fe ions, the Jahn–Teller relaxation slows down and the electric quadrupole shift increases. The magnetotransport phenomena of Zn _x Fe_1?x Cr₂S₄ is related to Jahn–Teller effect and half-metallic electronic structure, which are different from the double exchange interactions of the manganite La–Ca–Mn–O system or the triple exchange interactions of sulfospinel Cu _x Fe_1?x Cr₂S₄.     

Magnetic and transport properties of CuCr1−x VxS2 compounds

A comparison of experimental and calculated effective magnetic moments shows that the sulfur in CuCr_1−x V_xS₂ compounds has two different oxidation states, S¹⁻ and S²⁻, while the vanadium has a higher degree of oxidation (V³⁺) than the chromium (Cr²⁺). A model is proposed to explain the reduction in the activation energy for defect formation in the Cu-sublattice and the rise in the Cu⁺-cation conductivity when chromium is replaced by vanadium. Fiz. Tverd. Tela (St. Petersburg) 41, 1450–1451 (August 1999)     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Magnetic ordering in manganites substituted by chromium ions

NdMn_1?x Cr _x O₃ and Nd_0.6Ca_0.4Mn_1?x Cr _x O₃ solid solutions have been studied by neutron diffraction and magnetic measurements. NdMn_0.5Cr_0.5O₃ is found to have a magnetic structure consisting of an antiferromagnetic G-type component and a ferromagnetic component, which are caused by 3d ions. The magnetic moments of the neodymium ions are parallel to the ferromagnetic component. Nd_0.6Ca_0.4Mn_0.5Cr_0.5O₃ mainly has a G-type magnetic structure, and the magnetic moments of the neodymium ions are normal to the antiferromagnetism vector. Magnetic phase diagrams are plotted for both systems. They are interpreted on the assumption that the Mn³⁺-O-Cr³⁺ superexchange interactions are positive and the Mn⁴⁺-O-Cr³⁺ interactions are negative; the fact that manganese and chromium ions are not ordered in a crystal lattice is taken into account. Concentration magnetic phase transformations proceed through a two-phase state because of the internal chemical inhomogeneity of the solid solutions.     

Magnetic exchange interactions induced by Cr-doping in perovskite manganites

The effect of Cr-doping on the structural, magnetic and transport properties of perovskite manganites La_0.8Ca_0.2Mn_1−xCr_xO₃ (0≤x≤0.7) has been investigated. The Curie temperature (T_C) of the Cr-doped samples is almost unchanged up to 30% of Cr-doping. The Cr-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_C. The dc and ac magnetization data suggest that ferromagnetic clusters induced by double exchange interaction between Cr³⁺ and Mn³⁺ ions and antiferromagnetic components driven by Cr³⁺/Mn⁴⁺ and Cr³⁺/Cr³⁺ interactions are present in the Cr-doped system, which is supported by comparative studies on magnetic and transport properties of LaMnO_3+δ and LaMn_0.75Cr_0.25O_3+δ.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript> ions in ABO<Subscript>3</Subscript> (A = Sc,Lu, In) diamagnetic crystals

A magnetic resonance method is applied to the investigation of a number of isostructural diamagnetic compounds ABO₃ (A = Sc, Lu, In) with small additions of Cr³⁺ ions (S = 3/2) sufficient to observe single-ion spectra. It is shown that the resonance spectra for isolated Cr³⁺ ions can be described to a good accuracy by the ordinary axial spin Hamiltonian for 3d ions in octahedral oxygen environment. The parameters of the spin Hamiltonian are determined. It is established that Cr³⁺ ions in these crystals are characterized by easy-axis-type anisotropy.     

On the mixed valence of the chromium ions in the noncollinear ferrimagnetic spinels Mn1−xCuxCr2S4 (Where x = 0.85, 0.90, 0.95)

For the polycrystalline samples of Mn_1?xCu_xCr₂S₄ (x = 0.85, 0.90, 0.95) the magnetization was measured in the temperature range between 77 K and the Curie temperature, T_C, using a magnetic balance (Faraday's method) and pulsed magnetic fields up to 2.0 T. The magnetic susceptibility was measured between T_C and about 600 K. The Curie temperatures were obtained using the kink point method.In the temperature range between 4.2 and 77 K the magnetization was measured in stationary magnetic fields up to 14 T. The data indicate a noncollinear ferrimagnetic structure. The compounds under investigation can be treated as CuCr₂S₄ slightly doped with Mn, with a valence distribution Mn²⁺_1?xCu¹⁺_xCr³⁺_2?xCr⁴⁺_xS^2?₄.     

Electrical properties of perovskite-type La(Cr1−xMnx)O3+δ

Perovskite-type La(Cr_1−xMn_x)O_3+δ (0.0x1.0) was synthesized using a sol–gel process. The crystal structure of La(Cr_1−xMn_x)O_3+δ changes from orthorhombic to rhombohedral at x=0.6. The Mn⁴⁺ ion content increases monotonically in the range 0.2x1.0. The magnetic measurement of La(Cr_1−xMn_x)O_3+δ indicates that a Mn³⁺ ion is a high-spin state with (d)³(dγ)¹. The variation of the average (Cr, Mn)-O distance is explained by ionic radii of the Cr³⁺, the Mn³⁺, the Mn⁴⁺ ions. Since the log σT–1/T curve is linear and the Seebeck coefficient (α) is independent of temperature, it is considered that La(Cr_1−xMn_x)O_3+δ is a p-type semiconductor and exhibits the hopping conductivity.