Magnetic, electrical, and optical properties of electron-doped Ca1 − x LaxMnO3 − δ(x ≤ 0.12) single crystals

The magnetic, electrical, and optical properties of Ca_{1 ? x} La_xMnO_{3 ? δ}(x ≤ 0.12) manganite single crystals have been studied. The state with a spatially inhomogeneous electron distribution has been found. Interrelations between the electric and magnetic subsystems are analyzed. The obtained magnetic data show evidence for the formation of a G-type antiferromagnetic (G-AFM) phase with a spin-canted structure in the crystal with x = 0.05, for which the Curie and Néel temperatures are T _C = T _N(G) = 115 K. On cooling from the paramagnetic state, the crystals with x = 0.10 and 0.12 exhibit transitions from the paramagnetic to a C-type antiferromagnetic (C-AFM) phase in a part of the volume at T _N(C) = 150 and 200 K, and from the paramagnetic to the G-type antiferromagnetic (G-AFM) phase in the remaining volume at T _N(G) = 110 and 108 K, respectively. The onset of the C-type magnetic phase nucleation in crystals is observed at lower dopant (La) concentrations than in polycrystalline samples, which is explained by the deviation of single crystals from the stoichiometry with respect to oxygen. The magnetic phase transitions are manifested by anomalies in the electric resistance and magnetoresistance of doped crystals. An analysis of the electrical and optical properties of the samples shows evidence of (i) the formation of a charge energy gap in the C-AFM phase with retained paramagnetic metallic regions and (ii) the presence of ferromagnetic “metallic” droplets in the insulating G-AFM phase. The multiphase state of Ca_{1 ? x} La_xMnO_{3 ? δ} manganite single crystals featuring the coexistence of two magnetic phases, the regions with orbital/charge ordering, and the FM “metallic” droplets is related to a competition of exchange interactions by the superexchange and double exchange mechanisms.     

Room-temperature phase separation in weakly doped lanthanum manganites

The properties of single crystals of weakly doped lanthanum manganites La_1?xA_xMnO₃ (A = Ca, Ce, Sr; x = 0, 0.07?0.1) have been studied in the temperature range from 77 to 400 K. It is established that these lanthanum manganites exhibit (in addition to the well-known characteristic features observed in the region of the temperature of magnetic ordering) changes in the electrical and magnetic properties in the region of room temperature (T ≈ 270–300 K), which is about two times the Curie temperature (T ≈ 120–140 K) and is far from the temperature of structural transitions in the samples studied. The results are explained in terms of phase separation related to the formation of magnetic clusters in the nonconducting medium. The phase separation is caused by a gain in the exchange energy and by the development of elastic stresses in the crystal lattice and proceeds via combination of small-radius magnetic polarons into a large-size magnetic cluster containing several charge carriers. The short-range order in the cluster appears and the phase separation begins at a temperature T_ps, which is close to T_C ≈ 300 K, typical of doped conducting manganites. The results of magnetic measurements show that, as the temperature decreases from 300 to 190 K, the size of superparamagnetic droplets increases from about 8 to 15 Å.     

Second harmonic of magnetization and Cu magnetic system behavior at phase separation in moderately oxygenated single crystals of La2CuO4+x

The results on the nonlinear longitudinal response (second order uniform dynamic susceptibility χ₂(ω)) of two moderately doped La₂CuO_4+x single crystals in the temperature region of the phase separation of extra oxygen are reported. Large 2D-fragments (I≈7·10³ Å) of stoichiometric La₂CuO₄ are shown to be responsible for the signal in sample withT _ps>-T _N≈243 K. The signal of the crystal withT _ps<T _N≈272 K is due to oxygen-rich phase. Its peculiarities are related either to change and destruction of magnetic ordering in the course of the phase separation or to the ordering of the extra oxygen.     

Magnetic and transport properties of colossal magnetoresistance compound EuB<Subscript>6</Subscript>

The galvanomagnetic and magnetic properties of EuB₆ single crystal have been measured over wide temperature (1.8–300 K) and magnetic-field (up to 70 kOe) ranges, and the parameters of charge carriers and the characteristics of the magnetic subsystem are estimated in the paramagnetic and ferromagnetic (T < T _C ≈ 13.9 K) phases of this compound with strong electron correlations. In the temperature range T < T* ≈ 80 K, a magnetoresistance hysteresis Δρ(H)/ρ(0) is detected; it reaches a maximum amplitude of about 5% at T ≈ 12 K. The anomalies of charge transport observed in the temperature range T _C < T < T* are shown to be related to the magnetic scattering of charge carriers (m _eff = (15–30)m ₀, where m ₀ is the free-electron mass) that results from a short-range magnetic order appearing upon the formation of ferromagnetic nanoregions (ferrons).     

Effects of divalent alkaline earth ions on the magnetic and transport features of La0.65A0.35Mn0.95Fe0.05O3 (A = Ca, Sr, Pb, Ba) compounds

We have studied the magnetic and transport properties of Fe doped La_0.65A_0.35Mn_0.95Fe_0.05O₃ (A = Ca, Sr, Pb, Ba) manganites. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition (T_C) except the Pb doped sample which is insulating and ferromagnetic (FM) in the entire temperature range. The magnetization and T_C are decreased by decreasing the cation size on La site. The transition temperature and magnetic moment at 77 K is a maximum for Sr doped sample and is decreasing if we increase or decrease the cation size from Sr size. The maximum value of T_C and magnetic moment for Sr based sample is most likely due to the closer ionic sizes of La and Sr as compared to the other dopants (Ca, Pb, and Ba). We observed a spin freezing type effect in the Pb doped sample below 120 K in resistivity, ac susceptibility and in magnetization. This suggests that the AFM interactions introduced by the Fe are most effective in the Pb doped composition leading to increased competition between the FM and AFM interactions. This FM and AFM interaction generates some degree of frustration leading to the appearance of spin glass like phase whose typical magnetic behavior is studied for small ion when the metallic like behavior is lost.     

A study of the structural phase transition in strontium titanate single crystal by coherent and incoherent second optical harmonic generation

The surface phase transition in a SrTiO₃ crystal was studied by second optical harmonic generation. Nonlinear optical response singularities were observed at temperature T*=145 K, which was 40 K higher than the T_c structural phase transition temperature in the crystal volume. Nonlinear critical opalescence in the crystal volume caused by the presence of point defects was studied. The second harmonic field and the intensity of critical opalescence were calculated based on the phenomenological model of nonlinear optical processes with the use of the Landau theory of phase transitions.     

Anomalous magnetism and 209Bi nuclear spin relaxation in Bi4Ge3O12 crystals

The quadrupole ²⁰⁹Bi spin–spin and spin–lattice relaxation were studied within 4.2–300 K for pure and doped Bi₄Ge₃O₁₂ single crystals which exhibit, as was previously found, anomalous magnetic properties. The results revealed an unexpectedly strong influence of minor amounts of paramagnetic dopants (0.015–0.5 mol.%) on the relaxation processes. Various mechanisms (quadrupole, crystal electric field, electron spin fluctuations) govern the spin–lattice relaxation time T ₁ in pure and doped samples. Unlike T ₁, the spin–spin relaxation time T ₂ for pure and Nd-doped samples was weakly dependent on temperature within 4.2–300 K. Doping Bi₄Ge₃O₁₂ with paramagnetic atoms strongly elongated T ₂. The elongation, although not so strong, was also observed for pure and doped crystals under the influence of weak (～30 Oe) external magnetic fields. To confirm the conclusion about strong influence of crystal field effects on the temperature dependence of T ₁ in the temperature range 4.2–77 K, the magnetization vs. temperature and magnetic field was measured for Nd- and Gd-doped Bi₄Ge₃O₁₂ crystals using a SQUID magnetometer. The temperature behavior of magnetic susceptibility for the Nd-doped crystal was consistent with the presence of the crystal electric field effects. For the Gd-doped crystal, the Brillouin formula perfectly fitted the curve of magnetization vs. magnetic field, which pointed to the absence of the crystal electric field contribution into the spin–lattice relaxation process in this sample.     

Intrinsic inhomogeneities of low-doped lanthanum manganites in the paramagnetic temperature range

The nature of the electrical resistivity for low-doped lanthanum manganites is elucidated. The electrical resistivity is described by the Efros-Shklovskii law (lnρ √ (T ₀/T)^−1/2, where T ₀ √ 1/R _ls) in the temperature range from T* ≈ 300 K ≈ T _C (T _C is the Curie temperature for conducting manganites) to their T _C and is explained by the tunneling of carriers between localized states. The magnetoresistance is explained by a change in the size of localized states R _ls in a magnetic field. The patterns of change in R _ls with temperature and magnetic field strength determined from magnetotransport properties are satisfactorily described in the model of phase separation into small-radius metallic droplets in a paramagnetic matrix. The sizes R _ls and their temperature dependence have been estimated through magnetic measurements. The results confirm the existence of a Griffith phase. The intrinsic inhomogeneities produced by thermodynamic phase separation determine the electrical resistivity and magnetoresistance of lanthanum manganites.     

Paramagnetic-ferromagnetic and insulator-metal phase transitions in La<Subscript>0.88</Subscript>MnO<Subscript>2.95</Subscript>

We present the results a study of structure by neutron diffraction and data on the magnetic properties (linear and nonlinear (second and third order) susceptibilities) of polycrystalline La_0.88MnO_2.95. This compound exhibits an insulator-metal (IM) phase transition at T _IM ≈ 253 K (above the Curie temperature, T _C ≈ 244 K) and reveals colossal magnetoresistance. The crystal structure is found to be rhombohedral, and the space group is R3c. Analysis of magnetic properties shows that at T* ≈ 258 K > T _C , isolated paramagnetic clusters occur in the paramagnetic matrix; their concentration increases upon cooling. We observed no noticeable differences between the temperature evolution of the clustered state of this manganite with its insulator-metal transition and in the insulator La_0.88MnO_2.91. Possible scenarios of the paramagnet-ferromagnet and I-M transitions in a self-organized clustered structure are discussed.     

Linear expansion, phase separation, and magnetic inhomogeneities in La0.92Ca0.08MnO3

A relation of the thermal expansion with magnetic and magnetotransport properties has been revealed in La_0.92Ca_0.08MnO₃ single crystals in the paramagnetic state. The magnetotransport and lattice properties and the specific features in the neutron scattering characteristics of the La_0.92Ca_0.08MnO₃ single crystals have been explained by the phase separation in the paramagnetic state into magnetic inhomogeneities (clusters) with short-range (～10 Å) and long-range (>10² Å) orders. The performed investigations have demonstrated that the clusters are closely related to the crystal lattice and that the magnetic inhomogeneities in the paramagnetic region are correlated to T ～ 250–300 K ? TC.     

Effect of electron irradiation on the paramagnetic state of La0.67Ca0.33MnO3

The effect of point defects on the magnetic properties of La_0.67Ca_0.33MnO₃ polycrystals and single crystals has been studied. The magnetic susceptibility χ _dc of the initial samples and samples irradiated by electrons to the maximum dose F = 9 × 10¹⁸ cm^?2 has been measured in the temperature region 80 K < T < 650 K. Local variations of Mn-O-Mn bond angles and lengths result in a nonmonotonic dose dependence of the Curie temperature T _C. At high doses of electron irradiation, F ≥ 5 × 10¹⁸ cm^?2, the temperature of the transition from the ferromagnetic to polaron state in a single crystal is found to increase. In the paramagnetic region close to T _C, ferromagnetically ordered polarons are observed to exist, while at T > 1.2T _C, localization of e _g electrons initiates formation of paramagnetic polarons with a higher magnetic moment. Electron irradiation stimulates persistence of magnetic polarons up to higher temperatures T > 2T _C.     

Magnetostructural phase transitions in manganese arsenide single crystals

The effect of an external magnetic field with a strength up to 140 kOe on the phase transitions in manganese arsenide single crystals has been investigated. The existence of unstable magnetic and crystal structures at temperatures above the Curie temperature T _C = 308 K has been established. The displacements of manganese and arsenic atoms during the magnetostructural phase transition and the shift in the temperature of the first-order magnetostructural phase transition in a magnetic field have been determined. It has been shown that the magnetocaloric effect in a magnetic field of 140 kOe near the Curie temperature T _C is equal to ??T ?? 13 K. A model of the superparamagnetic state in MnAs above the temperature T _C has been proposed using the data on the magnetic properties and structural transformation in the region of the first-order magnetostructural phase transition. It has been demonstrated that, at temperatures close to T _C, apart from the contribution to the change in the entropy from the change in the magnetization there is a significant contribution from the transformation of the crystal lattice due to the magnetostructural phase transition.     

Second-order phase transition with coexistence of short-range and long-range ferromagnetic interactions in Ba1.7La0.3FeMoO6 compound

In this work, the magnetic properties and critical behavior around ferromagnetic–paramagnetic (FM–PM) phase transition in Ba_1.7La_0.3FeMoO₆ compound have been investigated in detail. This compound exhibits a second-order magnetic phase transition with Curie temperature T_C = 345 K. The critical exponents β, γ, and δ that are determined by using the modified Arrott plots (MAP), the Kouvel–Fisher (KF) and the critical isotherm analysis agree very well. Our results indicate a coexistence of short-range and long-range ferromagnetic (FM) interactions in Ba_1.7La_0.3FeMoO₆ compound. The existence of long-range FM interactions in this compound can be associated with the crystal structure of materials with long-range Fe/Mo ordering parameter and strength of double-exchange interaction, whereas the existence of the short-range FM interactions can be explained by magnetic inhomogeneity and FM clusters.     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.     

Fluctuations of the order parameter in R 0.55Sr0.45MnO3 manganites near the metal-insulator phase transition

The magnetic phase transformations induced by changes of the composition, external magnetic field strength, and temperature in manganites with a nearly half-filled conduction band in the vicinity of the metal-insulator phase transition have been investigated experimentally. It has been found that the substitution of rare-earth ions (Sm) for Nd ions with a larger ionic radius in R _0.55Sr_0.45MnO₃ manganites leads to a linear decrease in the Curie temperature T _C from 270 to 130 K and a transformation of the second-order ferromagnetic (FM) phase transition into a first-order phase transition. The results of measurements of the alternating-current (ac) magnetic susceptibility in the (Nd_{1 ? y} Sm _y )_0.55Sr_0.45MnO₃ system indicate the existence of a Griffiths-like phase in samples with a samarium concentration y > 0.5 in the temperature range T _C < T < T* (where T* ～ 220 K). For samples with y > 0.5, the magnetization isotherms at temperatures above T _C exhibit specific features in the form of reversible metamagnetic phase transitions associated with strong fluctuations of the short-range ferromagnetic order in the system of Mn spins in the high-temperature Griffiths phase consisting of ferromagnetic clusters. According to the results of measurements of the ac magnetic susceptibility in the (Sm_{1 ? y} Gd _y )_0.55Sr_0.45MnO₃ system for a gadolinium concentration y = 0.5, there is an antiferromagnetic (AFM) phase with an unusually low critical temperature of the spin ordering T _N ? 48.5 K. An increase in the external static magnetic field at 4.2 K leads to an irreversible induction of the ferromagnetic phase, which is stable in the temperature range 4.2–60 K. In the temperature range 60 K < T < 150 K, there exists a high-temperature Griffiths-like phase consisting of clusters (correlations) with a local charge/orbital ordering. The metastable antiferromagnetic structure is retained in samples with gadolinium concentrations y = 0.6 and 0.7, but it is destroyed with a further increase in the gadolinium concentration upon the transition to the spin-glass state. The magnetization isotherm obtained with variations in the external static magnetic field in the field range ±70 kOe at 4.2 K and the temperature dependence of the ac-magnetic susceptibility χ suggest that, in the Gd_0.55Sr_0.45MnO₃ ceramics, there is a mixed two-phase low-temperature state consisting of the quantum Griffiths phase with a characteristic divergence of χ(T) near T = 0, which was embedded in the spin-glass matrix with the spin “freezing” temperature T _G ? 42 K. The low-temperature state with quantum fluctuations exists in the (Sm_{1 ? y} Gd _y )_0.55Sr_0.45MnO₃ system for y ≥ 0.5.     

Sign reversal of the magnetoplastic effect in C60 single crystals during the sc-fcc phase transition

It is found that the magnetoplastic effect in C₆₀ single crystals in a pulsed magnetic field with induction larger than 10 T changes its sign in the vicinity of the phase transition at T _c =250–260 K: crystal strengthening is observed for T<T _c , and softening occurs for T>T _c . This indicates a change in the crystal lattice structure in the magnetic field.     

Effect of magnetic field on the TC and magnetic properties for the aligned MnBi compound

In the compound MnBi, a first-order transition from the paramagnetic to the ferromagnetic state can be triggered by an applied magnetic field and the Curie temperature increases nearly linearly with an increase in magnetic field by ∼2 K/T. Under a field of 10 T, T_C increases by 20 and 22 K during heating and cooling, respectively. Under certain conditions a reversible magnetic field or temperature induced transition between the paramagnetic and ferromagnetic states can occur. A magnetic and crystallographic H-T phase diagram for MnBi is given. Magnetic properties of MnBi compound aligned in a Bi matrix have been investigated. In the low temperature phase MnBi, a spin-reorientation takes place during which the magnetic moments rotate from being parallel to the c-axis towards the basal plane at ∼90 K. A measuring Dc magnetic field applied parallel to the c-axis of MnBi suppresses partly the spin-reorientation transition. Interestingly, the fabricated magnetic field increases the temperature of spin-reorientation transition T_s and the change in magnetization for MnBi. For the sample solidified under 0.5 T, the change in magnetization is ∼70% and T_s is ∼91 K.     

Critical nuclear relaxation in cobalt metal

Nuclear magnetic resonance of cobalt metal was investigated in the paramagnetic and ferromagnetic states and in the critical region below T_c. The Knight shift and spin lattice relaxation times were measured in the paramagnetic phase in the solid and liquid states from 1578 K to 1825 K. The resonant frequency, spin-lattice and spin-spin relaxation times were measured in the ferromagnetic phase from room temperature to 1385 K. The main part of (T₁T)^-1 results from fluctuating orbital moments in both phases except near T_c where this process forms the background for critical spin relaxation. The critical exponents for T^-1₁ and for the magnetization in the ferromagnetic state were found to be n' = 0.96 ± 0.07 and β = 0.308 ± 0.012, respectively.     

Thermal and magnetic properties of DyB62 at low temperatures

Temperature dependences of heat capacity C_P(T) and magnetization M(T) of an icosahedral dysprosium boride (DyB₆₂) single crystal have been experimentally investigated in the temperature range of 2-300 K. The magnetic susceptibility χ(T) of DyB₆₂ follows Curie-Weiss law with a paramagnetic Curie temperature of −3.7 K, which implies that the antiferromagnetic interactions are dominant in this material and suggests the possibility of magnetic ordering at low temperatures. This conjecture is supported by the temperature dependence of heat capacity C_P(T), which decreases upon heating from 2 to 7 K. The heat capacity of DyB₆₂ at 2 K is analyzed as a sum of magnetic, Debye, two-level system and soft atomic potential components.     

The effect of Ru doping on the alkali-doped manganite Pr0.8Na0.2MnO3

Polycrystalline manganites Pr_0.8Na_0.2MnO₃ doped by ruthenium (0.0≤x_Ru≤0.2) were prepared by the sol-gel process. The magnetic field induced metamagnetism was observed to occur with a large resistivity drop at 3 K for x_Ru≤0.02 samples, which can be sorted into the kind of CMR phenomenon. It was found that the 0.01 Ru doping increased T_C and decreased the metamagnetic critical field than that of the undoped sample. The doped manganites show a quick increase in their magnetic moments as x_Ru increases from 0.01 to 0.04, but the larger fraction of Ru doping (0.04≤x_Ru≤0.2) reduces their M and T_C. All the five doped samples have larger magnetic moments than that of the host sample. Ru doping of x_Ru>0.01 results in a rapid disappearance for the observation of long range spin and charge ordering in the samples’ M-T curves, which is characteristic of the undoped sample. It was found that larger low-temperature MR favored decrease in the metamagnetic critical field. Finally, the phase diagram of Ru doping vs. transition temperatures is presented to summarize the experiments.