R. Szymczak

Magnetic and electrical properties of the ZnGeAs(2): Mn chalcopyrite

Doping of the ZnGeAs2 semiconductor with manganese has produced compositions with spontaneous magnetization and high Curie temperatures of up to 367 K for the composition 3.5 wt% Mn. Their magnetic properties are characteristic of spin glasses at temperatures T < TS and magnetic fields H < 11 kOe. In stronger fields, the spin glass state transforms into a phase with a spontaneous magnetization 4–5 times weaker than that to be expected under ferromagnetic ordering of all Mn ions. This is obviously a singly-connected ferromagnetic phase containing regions with frustrated bonds. The frustrated regions and the spin glass phase have inclusions of noninteracting ferromagnetic clusters, because these regions and the spin glass phase at low temperatures exhibit a strong increase in the magnetization M, with the dependence M(T) being described by the Langevin function. Measurements of the electrical resistivity ρ and the Hall effect have revealed that, for T < 30 K, the resistivity ρ of compositions with 1.5 and 3.5 wt % Mn is higher that at 30 K, which makes superexchange dominant and gives rise to the onset of the spin glass state. The nonuniform distribution of Mn ions in the spin glass phase accounts for the existence of isolated ferromagnetic clusters, their ferromagnetism being generated by carrier-mediated exchange. As the temperature increases still more, the increase in the mobility occurs faster than the decrease in the concentration, thus promoting an enhancement of the carrier-mediated exchange and growth of the ferromagnetic clusters in size, which at T = TS come in contact. This signifies a transition from a multiply-to a singly-connected ferromagnetic phase, which contains microregions with frustrated bonds.

A new High-Tc ferromagnet: Manganese-doped CdGeAs2 chalcopyrite

New ferromagnets with high Curie temperatures, reaching 355 K, have been obtained by doping a GdGeAs2 semiconductor compound with manganese. The obtained compounds are magnetically inhomogeneous, comprising a mixture of ferromagnetic (FM) and paramagnetic phases. The volume fraction of the FM phase increases with the degree of doping. The development of ferromagnetism in this system is probably related to the presence of vacancies of the (Cd, VC, Mn)GeAs2 type or to a nonstoichiometry of the (Cd, Ge, Mn)GeAs2 type, since theoretical estimates show that the FM state is energetically more favorable than the spin glass state only in these cases.

Manganese-doped ZnSiAs2 chalcopyrite: A new advanced material for spintronics

A new spintronics material with the Curie temperature above room temperature, the ZnSiAs2 chalcopyrite doped with 1 and 2 wt % Mn, is synthesized. The magnetization, electrical resistivity, magnetoresistance, and the Hall effect of these compositions are studied. The temperature dependence of the electrical resistivity follows a semiconducting pattern with an activation energy of 0.12–0.38 eV (in the temperature range 124 K ≤ T ≤ 263 K for both compositions). The hole mobility and concentration are 1.33, 2.13 cm2/V s and 2.2 × 1016, 8 × 1016 cm−3 at T = 293 K for the 1 and 2 wt % Mn compositions, respectively. The magnetoresistance of both compositions, including the region of the Curie point, does not exceed 0.4%. The temperature dependence of the magnetization M(T) of both compositions exhibits a complicated character; indeed, for T ≤ 15 K, it is characteristic of superparamagnets, while for T > 15 K, spontaneous magnetization appears which correspond to a decreased magnetic moment per formula unit as compared to that which would be observed upon complete ferromagnetic ordering of Mn2+ spins or antiferromagnetic ordering of spins of the Mn2+ and Mn3+ ions. Thus, for T > 15 K, it is a frustrated ferro- or ferrimagnet. It is found that, unlike the conventional superparamagnets, the cluster moment μc in these compositions depends on the magnetic field: ∼12000–20000μB for H = 0.1 kOe, ∼52–55μB for H = 11 kOe, and ∼8.6–11.0μB at H = 50 kOe for the compositions with 1 and 2 wt % Mn, respectively. The specific features of the magnetic properties are explained by the competition between the carrier-mediated exchange and superexchange interactions.

Ferromagnetic semiconductor ZnGeAs2 {Mn} with a curie point of 367 K

Germanium zinc diarsenide crystals with various manganese fractions, (ZnGeMn)As2, were prepared by reacting high-purity powders of zinc diarsenide, germanium, arsenic, and manganese. The manganese solubility at temperatures near the ZnGeAs2 melting temperature was 3.5 wt % as determined by X-ray fluorescence analysis. The unit cell volume decreased with rising manganese concentration. Magnetization in fields up to 50 kOe, magnetic susceptibility, electrical resistance, and Hall constants were measured over wide temperature ranges. Manganese-doped samples had spontaneous magnetization and high Curie temperatures reaching 367 K. Their magnetic properties are characteristic of spin glasses in low magnetic fields. In higher fields, the spin state changed to spontaneous magnetization.

Synthesis and magnetic properties of Cu3B2O6 single crystals

The temperature dependence of the magnetic susceptibility of Cu3B2O6 single crystals grown by spontaneous crystallization from a melt consisting of a mixture of CuO and B2O3 and the behavior of their magnetization are investigated in magnetic fields up to 55 kOe. A broad susceptibility maximum is observed near 39 K, and a sharp drop in susceptibility is observed at T<10 K. The paramagnetic Néel temperatures for all orientations of the magnetic field in the crystal investigated are negative, attesting to the predominantly antiferromagnetic character of the exchange interactions. The effective magnetic moment of the Cu2+ ion is anisotropic and lies in the range from 1.054μB to 1.545μB. The magnetization depends linearly on magnetic field at T>10 K, whereas at temperatures below 10 K a discontinuity is observed at fields of the order of 40 kOe. At room temperature, electron magnetic resonance characterized by an almost isotropic g factor (g=2.165) is detected at 36.22 GHz. The exchange interactions in Cu3B2O6 are analyzed on the basis of the Goodenough-Kanamori rules. The possibility of the establishment of a singlet magnetic state in the crystal is analyzed.

Spectroscopic and magnetic properties of two di-copper(II) complexes with macrocyclic schiff bases

Abstract Two binuclear copper(II) complexes with macrocyclic Schiff bases Cu2LI(CH3COO)2·5H2O (complex I) and Cu2LII(CH3COO)2·2H2O (complex II) were synthesized and then characterized by IR, UV, and thermogravimetric analysis (TGA) measurements. TGA was used to investigate the desolvation of lattice water molecules. IR spectra demonstrated the formation of the cyclic compound and together with chemical elemental analysis were used to propose the structure of the complexes. The UV spectra of both complexes are typical for binuclear copper(II) complexes with Robson-type ligands. Variable-temperature magnetic susceptibility measurements corroborated by EPR and low-temperature isothermal magnetization data confirmed the formation of copper dimers with antiferromagnetic exchange coupling constants of −400 and −1250 cm−1 for complexes I and II, respectively, residing outside the usual range for the phenoxide bridged Cu(II) complexes. This implies the possibility that additional superexchange paths through the macrocyclic ligand may affect the intradimer exchange interaction as well as the phenoxide oxygen bridges.

Magnetic and electric properties of manganese-doped ZnSiAs2

A new p-type dilute magnetic semiconductor was synthesized on the basis of manganese-doped ZnSiAs2 chalcopyrite. As the manganese percentage in ZnSiAs2 increased, the Curie temperature increased from 325 to 337 K for compositions containing 1 and 2 wt % manganese. The ferromagnetic properties of the new dilute magnetic semiconductor were due to nanoclusters that were generated by concurrent substitution of manganese for elements in the cationic sublattice of chalcopyrite.

Novel ferromagnetic Mn-doped ZnSiAs2 chalcopyrite with Curie point exceeded room temperature

Based on Mn-doped chalcopyrite ZnSiAs2 the new dilute magnetic semiconductor with p-type conductivity was produced. The Curie temperature behavior of the produced semiconductor is distinctly dependent on the Mn concentration: 325 K for 1 wt.% and 337 K for 2 wt.% of Mn, consequently. Magnetization, electrical resistance, magnetic resistance and Hall effect of mentioned compositions were studied. Temperature dependence of magnetization M(T) have complicate behavior. For T uf0a3 15 K the M(T) dependence is characteristic for superparamagnetic and at T > 15 K magnetization is sum of magnetizations of ensemble of superparamagnetic clusters and ferromagnetic phase contained frustration regions.

Magnetic, electrical, and crystallographic properties of thin La1−xSrxMnO3 films

A study is reported of the magnetic, electrical, and crystallographic properties of La1−xSrxMnO3 (0.15⩽x⩽0.23) epitaxial films grown on single-crystal substrates of (001)ZrO2(Y2O3) having the fluorite structure and (001)LaAlO3 having the perovskite structure. It was found that films with close compositions for x=0.15 and 0.16, grown on different substrates, have different properties, namely, the film on a fluorite substrate is semiconducting and has a coercive strength 30 times that of the film on a perovskite substrate; the temperature dependence of electrical resistance of the latter film has a maximum around the Curie point TC and follows metallic behavior for T<TC. These differences are explained as due to different structures of the films. The x=0.23 film on the perovskite substrate has been found to exhibit a combination of giant magnetoresistance at room temperature with a resistance of ≈300 Ω which is useful for applications. The maxima in resistance and absolute value of negative magnetoresistance are accounted for by the existence of two-phase magnetic states in these films.

Manganese-doped CdGeAs2, ZnGeAs2 and ZnSiAs2 chalcopyrites: a new advanced materials for spintronics

Based on the Mn-doped chalcopyrites CdGeAs2, ZnGeAs2 and ZnSiAs2, new dilute magnetic semiconductors with the p-type conductivity were produced. Magnetization, electrical resistivity and Hall effect of these compositions were studied. Their temperature dependences of magnetization are similar in form in spite of a complicated character, which is controlled by the concentration and mobility of the charge carriers. Thus, for T < 15 K, these curves are characteristic of superparamagnets and for T > 15 K, of a frustrated ferromagnet. In compounds with Zn these two states are diluted by a spinglass-like state. This specific feature is ascribed to attraction of Mn ions occupying neighboring sites and to competition between the carrier-mediated exchange and superexchange interactions. The Curie temperatures of these compounds are above room temperature. These are the highest Curie temperatures in the AIIBIVCV2:Mn systems.