Ferrimagnetic Ordering and Spin-Glass State in Diluted GdFeO3-Type Perovskites (Lu0.5Mn0.5)(Mn1-xTix)O3 with x = 0.25, 0.50, and 0.75.

ABO3 perovskite materials with small cations at the A site, especially those with ordered cation arrangements, have attracted a great deal of interest because they show unusual physical properties and deviations from the general characteristics of perovskites. In this work, perovskite solid solutions (Lu0.5Mn0.5)(Mn1-xTix)O3 with x = 0.25, 0.50, and 0.75 were synthesized by means of a high-pressure, high-temperature method at approximately 6 GPa and approximately 1550 K. All the samples crystallize in the GdFeO3-type perovskite structure (space group Pnma) and have random distributions of the small Lu3+ and Mn2+ cations at the A site and Mn4+/3+/2+ and Ti4+ cations at the B site, as determined by Rietveld analysis of high-quality synchrotron X-ray powder diffraction data. Lattice parameters are a = 5.4431 Å, b = 7.4358 Å, c = 5.1872 Å (for x = 0.25); a = 5.4872 Å, b = 7.4863 Å, c = 5.2027 Å (for x = 0.50); and a = 5.4772 Å, b = 7.6027 Å, c = 5.2340 Å (for x = 0.75). Despite a significant dilution of the A and B sublattices by non-magnetic Ti4+ cations, the x = 0.25 and 0.50 samples show long-range ferrimagnetic order below TC = 89 K and 36 K, respectively. Mn cations at both A and B sublattices are involved in the long-range magnetic order. The x = 0.75 sample shows a spin-glass transition at TSG = 6 K and a large frustration index of approximately 22. A temperature-independent dielectric constant was observed for x = 0.50 (approximately 32 between 5 and 150 K) and for x = 0.75 (approximately 50 between 5 and 250 K).

Temperature evolution of 3d- and 4f-electron magnetic ordering in the ferrimagnetic Mn self-doped perovskite (Yb0.667Mn0.333)MnO3.

A high-pressure synthesis method was employed to prepare Mn-self-doped perovskites (R0.667Mn0.333)MnO3(R= Yb, Lu) at about 6 GPa and 1670 K. Crystal and magnetic structures of (Yb0.667Mn0.333)MnO3have been studied by combining neutron powder diffraction, magnetic susceptibility and specific heat measurements. Within the orthorhombic space groupPnma, magnetic cations are located on site 4c(A site, occupied by two thirds of Yb3+and one third of Mn2+) and on site 4b(B site, occupied by two thirds of Mn3+and one third of Mn4+). The degree of structural distortion of the MnO6octahedra follows the general trend of (R1-xMnx)MnO3compounds which shows a decrease with increasing amount of Jahn-Teller inactive Mn4+cations. Mn-Mn interactions produce a collinear ferrimagnetic structure (TC,Mn= 106 K) with ferromagnetically ordered Mn moments at the B site being coupled antiferromagnetically with ordered Mn moments at the A site. Mn-Yb interactions induce a small but non-zero ferromagnetic Yb3+moment which can explain a small decrease of the magnetic susceptibility at low temperature. Yb-Yb interactions create an antiferromagnetic structure atTN,Yb≈ 40 K. Ordered moments of the ferrimagnetic and antiferromagnetic structures are oriented perpendicular to each other within theac-plane and Yb3+moments contribute to both structures. The appearance of ordered Yb3+moments induced by Mn-Yb interactions in perovskite (Yb0.667Mn0.333)MnO3is a result of the Mn self-doping on the A site and has not been observed in the orthorhombic perovskite modification (space groupPnma) of the undoped parent compound YbMnO3, but interestingly, it also appears in the hexagonal non-perovskite modification (space groupP63cm) of YbMnO3.

Crystal and Magnetic Structures and Properties of (Lu1- xMn x)MnO3 Solid Solutions.

(Lu1- xMn x)MnO3 solid solutions, having the perovskite-type structure and Pnma space group, with 0 ≤ x ≤ 0.4 were synthesized by a high-pressure, high-temperature method at 6 GPa and about 1670 K from Lu2O3 and Mn2O3. Their crystal and magnetic structures were studied by neutron powder diffraction. The degree of octahedral MnO6 tilting decreases in (Lu1- xMn x)MnO3 with increasing x. Only the incommensurate (IC) spin structure with a propagation vector of k = ( k0, 0, 0) and k0 ≈ 0.44 remains in (Lu0.9Mn0.1)MnO3 in the whole temperature range below the Neel temperature TN = 36 K, and the commensurate noncollinear E-type structure that has been reported in the literature for undoped o-LuMnO3 is not observed. (Lu1- xMn x)MnO3 samples with 0.2 ≤ x ≤ 0.4 have a ferrimagnetic structure with a propagation vector of k = (0, 0, 0) and ferromagnetic (FM) ordering of Mn3+ and Mn4+ cations at the B site, which are antiferromagnetically coupled to a noncollinear predominantly FM arrangement of Mn2+ at the A site. The ferrimagnetic Curie temperature, TC, increases monotonically from 67 K for x = 0.2 to 118 K for x = 0.4. Magnetic and dielectric properties of (Lu1- xMn x)MnO3 and a composition-temperature phase diagram are also reported.

Mn Self-Doping of Orthorhombic RMnO3 Perovskites: (R0.667Mn0.333)MnO3 with R = Er-Lu.

Orthorhombic rare-earth trivalent manganites RMnO3 (R = Er-Lu) were self-doped with Mn to form (R0.667Mn0.333)MnO3 compositions, which were synthesized by a high-pressure, high-temperature method at 6 GPa and about 1670 K from R2O3 and Mn2O3. The average oxidation state of Mn is 3+ in (R0.667Mn0.333)MnO3. However, Mn enters the A site in the oxidation state of 2+, creating the average oxidation state of 3.333+ at the B site. The presence of Mn2+ was confirmed by hard X-ray photoelectron spectroscopy measurements. Crystal structures were studied by synchrotron powder X-ray diffraction. (R0.667Mn0.333)MnO3 crystallizes in space group Pnma with a = 5.50348(2) Å, b = 7.37564(1) Å, and c = 5.18686(1) Å for (Lu0.667Mn0.333)MnO3 at 293 K, and they are isostructural with the parent RMnO3 manganites. Compared with RMnO3, (R0.667Mn0.333)MnO3 exhibits enhanced Néel temperatures of about TN1 = 106-110 K and ferrimagnetic or canted antiferromagnetic properties. Compounds with R = Er and Tm show additional magnetic transitions at about TN2 = 9-16 K. (Tm0.667Mn0.333)MnO3 exhibits a magnetization reversal or negative magnetization effect with a compensation temperature of about 16 K.

Anisotropic magnetic properties and magnetic structure of YbPdSi.

YbPdSi with orthorhombic crystal structure (space group Pmmn) exhibits a magnetic transition at [Formula: see text] K, below which a ferromagnetic moment develops with an enhanced electronic specific-heat coefficient [Formula: see text] mJ K(-2) mol(-1). We have investigated the magnetization, electrical resistivity, and specific heat of YbPdSi using single crystalline samples as functions of temperature and magnetic field. It has been found that the ferromagnetic moment points to the c-direction, although the magnetic moments have an Ising-like anisotropy along the b-direction above the magnetic-transition temperature. Field dependence of the magnetization and electrical resistivity shows a metamagnetic-like transition at [Formula: see text] T when field is applied along the b-axis below T = 3 K, suggesting the existence of an antiferromagnetic component along this direction. The magnetic structure has been investigated by neutron diffraction using powder samples. The magnetic unit cell is identical to the crystal unit cell. The Rietveld fitting has revealed that Yb at the 2a and 2b positions exhibit a collinear ferromagnetic order along the c-axis, whereas Yb at the 4e position undergoes a non-collinear order, involving the ferromagnetic moment along the c-axis and an antiferromagnetic component along the b-axis. The ferromagnetic moments determined by the neutron diffraction are 0.26, 1.3, and 0.15 [Formula: see text] for Yb at the 4e, 2b, and 2a sites, respectively. The reduced moments for the 4e and the 2a sites suggest that the Kondo screening effect is important in YbPdSi.

Magnetic structure of the ferromagnetic Kondo-lattice compounds YbPtGe and YbPdGe.

YbPtGe and YbPdGe exhibit ferromagnetic ordering below Tc = 5.4 and 11.4 K with enhanced electronic specific heat coefficients of γ = 209 and 150 mJ K(-2) mol, respectively. In order to shed light on the origin of the coexistence of a ferromagnetic state and heavy-fermion behavior, we studied the powder neutron diffraction of YbPtGe and YbPdGe at low temperatures. Weak reflections due to magnetic ordering have been resolved. The data were analyzed using the Rietveld method together with group theory analysis. It has been found that YbPtGe exhibits a non-collinear ferromagnetic structure, with a spontaneous moment along the c-axis and a weak antiferromagnetic component along the a-axis. The presence of this antiferromagnetic component explains the origin of the observed metamagnetic-like behavior. In the case of YbPdGe, magnetization measurements confirmed the ferromagnetic moment along the b-axis and revealed a metamagnetic transition at 0.2 T for a field parallel to the c-axis. The neutron diffraction results indicate that the magnetic structure of YbPdGe is also of a non-collinear type, with ferromagnetic moments parallel to the b-axis and weak antiferromagnetic components along the c-axis, which is consistent with the magnetization data. A comparison of the results for YbPtGe and YbPdGe has been made. It is suggested that both the Kondo screening effect of ferromagnetic moments and the fluctuation of antiferromagnetic components can contribute to the enhanced mass in the ferromagnetic state.