Magnetic and transport properties of RCr0.3Ge2 (R=Tb, Dy, Ho and Er) compounds

The magnetic and transport properties of ternary rare-earth chromium germanides RCr_0.3Ge₂ (R=Y and Tb-Er) have been determined. X-ray and neutron diffraction studies indicate that these compounds have the CeNiSi₂-type structure (space group Cmcm) [1]. Magnetic measurements reveal the antiferromagnetic ordering below T_N equal to 18.5 K (R=Tb), 11.8 K (Dy), 5.8 K (Ho) and 3.4 K (Er). From the neutron diffraction data the magnetic structures have been determined. For TbCr_0.3Ge₂ and DyCr_0.3Ge₂ at low temperatures the magnetic ordering can be described by two vectors k₁=(,0,0) and k₂=(,0,), and k₁′=(,0,0) and k₂′=(,0,), respectively. In HoCr_0.3Ge₂ and ErCr_0.3Ge₂ the ordering can be described by one propagation vector equal to (,,0) and (0,0,0.4187(2)), respectively. In DyCr_0.3Ge₂ some change in the magnetic ordering is observed at T_t=5.1 K. In temperature range from T_t to T_N the magnetic ordering is given by one propagation vector k=(,0,0). YCr_0.3Ge₂ is a Pauli paramagnet down to 1.72 K which suggests that in the entire RCr_0.3Ge₂ series the Cr atoms do not carry magnetic moments. All compounds studied exhibit metallic character of the electrical conductivity. The temperature dependencies of the lattice parameters reveal strong magnetostriction effect at the respective Nèel temperatures.     

Ferrimagnetism in the rare earth titanium (III) oxides, RTiO3; R = Gd,Tb, Dy,Ho, Er,Tm

The series of compounds RTiO₃, R = Gd, Tb, Dy, Ho, Er, and Tm, were obtained as single-phase materials via solid state reaction between Ti₂O₃ and R₂O₃ at ca. 1500°C in welded molybdenum crucibles under argon; YbTiO₃ and LuTiO₃ could not be obtained as single-phase materials using this procedure. Lattice constants for all compounds were determined from powder X-ray data and are compared with previous results. All of these materials order magnetically between 30 and 70 K. From the appearance of the χ^?1_m vs T curve the type of order can be identified as ferrimagnetic. High-temperature susceptibility data have been fit to a two-sublattice molecular field model and the intra- and intersublattice interaction constants have been extracted. It is found that the TiTi interaction is ferromagnetic and relatively constant from R = Gd to R = Lu. Low-temperature magnetization field data suggest the existence of complex magnetic structures, large magnetocrystalline anisotropy, or both. The magnetic properties of the RTiO₃ series are compared to those of the chemically similar and better-known RMO₃ phases where M = Al, V, Cr, Mn, and Fe. The observed differences are shown to follow from the sign of the M-M interaction, which is ferromagnetic for M = Ti and antiferromagnetic for M = V, Cr, Mn, and Fe, together with the implications of the crystal symmetry for the R-M interaction.     

Heat capacity and thermodynamic functions of theRFe2 compounds (R =Gd,Tb, Dy,Ho, Er,Tm, Lu) over the temperature region 8 to 300 K

Experimental heat capacity data for the Laves phaseRFe₂ intermetallic compounds (R =Gd, Tb, Dy, Ho, Er, Tm, and Lu) have been determined over the temperature range 8 to 300 K. The error in these data is thought to be less than 1%. Smoothed heat capacity values and the thermodynamic functions, (H°_T ? H°₀) and S°_T, are reported throughout the temperature range for theRFe₂ series. In addition, (G°₂₉₈ ? H°₀) at 298 K is reported for all theRFe₂ compounds. These data were analyzed and it was shown that the maxima in the thermodynamic functions near HoFe₂ are due to the magnetic contribution of the lanthanide element. The lattice contribution to the entropy at 300 K was estimated, and from this quantity the Debye temperature was calculated to be about 300 K, which is in good agreement with the low-temperature heat capacity. Furthermore, this analysis indicates that the apparent electronic specific heat constants, γ′, for TbFe₂, DyFe₂, and HoFe₂, reported earlier, are in error.     

Field-Induced Magnetic Properties in RCrO4 Oxides (R=Pr, Gd, Tb, Tm, and Yb)

RCrO₄ oxides (R=Pr, Gd, Tb, Tm, and Yb) have been synthesized at 773 K using the corresponding nitrates as precursors. X-ray diffraction data reveal that these samples are single phases and crystallize with the zircon-type structure, showing tetragonal symmetry, space group I4₁/amd. All the compounds are antiferromagnetic and the Néel temperature, which depends on the R³⁺ ion, takes values lower than 30 K. The presence of a canting appears to be responsible for the negative values of the magnetic susceptibility found below the compensation temperature. This uncommon phenomenon is named reversal of magnetization. It is field-dependent, being suppressed at 500 Oe for the TmCrO₄ compound. The highest value of the compensation temperature (24 K) corresponds to the YbCrO₄ oxide. A metamagnetic transition has been observed in all cases at critical fields ranging from 225 Oe (GdCrO₄) to 1600 Oe (YbCrO₄).     

Subsolidus phase relations and crystal structures of R-Ca-Cu-O (R=Nd, Sm, Gd, Tm) systems

The subsolidus phase relations of R₂O₃-CaO-CuO ternary systems (R=Nd, Sm, Gd, Tm) have been investigated by X-ray powder diffraction. All samples were synthesized at about 950° in air. There exists a ternary compound Ca_14−xR_xCu₂₄O₄₁ (x = 4 for R=Nd, Gd and x = 5 for R = Sm) and a ternary solid solution Ca_2+xR_2−xCu₅O₁₀ (R=Nd, Sm, Gd, Tm) with a wide composition range Δx of about 0.6. The compound Ca_14−xR_xCu₂₄O₄₁ possesses a layered orthorhombic structure and is isostructural to Sr_14−xCa_xCu₂₄O₄₁. The lattice parameters a and c of the compound are basically independent of the ionic radius of R, while the lattice parameter b and unit-cell volume V decrease substantially with the decrease of the ionic radii of R. The Ca_2+xR_2−xCu₅O₁₀ solid solution is isostructural to Ca_2+xY_2−xCu₅O₁₀, the structure of which is based on an orthorhombic “NaCuO₂-type” subcell containing infinite one-dimensional chains of edge-shared square planar cuprate groups crosslinked by the layered cations Ca and R that locate in the inter-chain tunnels.     

Exchange interactions in R2Fe17−xGax (R=Y, Sm, Gd, Tb, Ho and Tm) compounds

We calculated the molecular field coefficients, n_FeFe and n_RFe (R=Sm, Gd, Tb, Ho and Tm), for R₂Fe_17−xGa_x and the values of n_FeFe and n_SmFe for R₂Fe_17−xT_x (T=Al and Si) using the experimental values of the Curie temperature. The values of n_FeFe increase in spite of the decrease of μ_Fe for 0?x?5. The values of n_SmFe have large values when the magnetic anisotropy is axial. For 6?x?8, the values of n_FeFe, n_HoFe and n_TmFe increase largely, which is related to the change of the easy magnetization direction. For Y₂Fe_17−xT_x (T=Ga and Al), the values of n_FeFe have a maximum value with increasing those of μ_Fe. With increasing V⁻¹, the values of n_FeFe have a maximum value around the same value of V⁻¹ for Y₂Fe_17−xT_x (T=Ga and Al). For Y₂Fe_17−xSi_x, the values of n_FeFe increase with increasing V⁻¹.     

Crystal structures of RPt3−xSi1−y(R=Y, Tb, Dy, Ho, Er, Tm, Yb) studied by single crystal X-ray diffraction

The crystal structures of ternary compounds RPt_3−xSi_1−y(R=Y, Tb, Dy, Ho, Er, Tm, Yb) have been elucidated from X-ray single crystal CCD data. All compounds are isotypic and crystallize in the tetragonal space group P4/mbm. The general formula RPt_3−xSi_1−y arises from defects: x≈0.20, y≈0.14. The crystal structure of RPt_3−xSi_1−y can be considered as a packing of four types of building blocks which derive from the CePt₃B-type unit cell by various degrees of distortion and Pt, Si-defects.     

Structure and magnetic properties of ScFe6Ga6-type RCo5Ga7 (R=Y, Tb, Dy, Ho and Er)

The structure and magnetic properties of the RCo₅Ga₇ (R=Y, Tb, Dy, Ho and Er) compounds with the ScFe₆Ga₆-type structure have been studied. The stability of RCo₅Ga₇ is closely related with the ratio of the metal radii R_RE/R_(Co,Ga). With R_RE/R_(Co,Ga)?1.36, the compounds can be stabilized in the ScFe₆Ga₆-type structure. The lattice of RCo₅Ga₇ shrinks as the atomic order of R increases, and it is consistent with the lanthanide contraction. The structure analysis based on X-ray diffraction patterns reveals that in the orthorhombic RCo₅Ga₇ (Immm), R occupies the 2a site, and Co enters into the 8k and the 4h sites, and Ga is at the 4e, 4f, 4g, 4h and 8k sites. The interatomic distances and the coordination numbers of RCo₅Ga₇ are provided from the refinement results. The short interatomic distance (less than 2.480 Å) between the Co ions results in the negative magnetic interaction, which does not favor ferromagnetic ordering. The magnetic moment of YCo₅Ga₇ is absent, and RCo₅Ga₇ (R=Tb, Dy, Ho and Er) may have long-range magnetic ordering with the paramagnetic Curie temperature lower than 5 K.     

Structure and physical properties of ternary rare-earth cobalt bismuth intermetallics (RE)12Co5Bi (RE = Y, Gd, Tb, Dy, Ho, Er, Tm)

The rare-earth intermetallic compounds (RE)12Co5Bi (RE = Y, Gd, Tb, Dy, Ho, Er, Tm) were prepared by arc-melting and annealing at 600 degrees C. These compounds extend the previously known (RE)6M2+xX1-x (M = Co, Ni; X = Ga, In, Sn, Pb) series with the Ho6Co2Ga-type structure to X = Bi. The crystal structure of Ho12Co5Bi was refined by the Rietveld method from powder X-ray diffraction data obtained using synchrotron radiation (Pearson symbol oI36, orthorhombic, space group Immm, Z = 2, a = 9.37598(14) A, b = 9.37871(14) A, c = 9.85465(13) A). Unlike other Ho6Co2Ga-type compounds, the 2a site in Ho12Co5Bi is exclusively occupied by Co atoms. Four-probe electrical resistivity measurements on sintered polycrystalline samples of (RE)12Co5Bi indicated metallic behavior. Magnetic measurements revealed behavior ranging from frequency-dependent maxima in the ac susceptibility for Y12Co5Bi to possible ferrimagnetic ordering for Gd12Co5Bi to antiferromagnetic ordering with metamagnetic transitions for the remaining compounds. As confirmed by band structure calculations using Y12Co5Bi as a model compound, Y-Y and Y-Co interactions are the most important bonding components, but matrix effects are likely responsible for anomalously short Co-Co contacts in the structure.     

Preparation and structural study from neutron diffraction data of R2MoO6 (R=Dy, Ho, Er, Tm, Yb, Y)

The title compounds have been prepared as polycrystalline powders by thermal treatments of stoichiometric mixtures of R₂O₃ and MoO₃ in air. The room-temperature crystal structure for all the series has been refined from high-resolution neutron powder diffraction data. All the phases are isostructural (space group C2/c, Z=8) with the polymorph α-R₂MoO₆, typified by Sm₂MoO₆. The structure contains four zigzag, one-dimensional MoO₅ polyhedral rows per unit cell, running through the RO₈ polyhedral framework along the [001] direction. MoO₅ form discrete units (i.e. do not share common oxygen), with Mo-O distances ranging from 1.77 to 2.24 Å, although the oxygen coordination can be extended to distances of about 3.1 Å, giving rise to strongly distorted MoO₈ scalenohedra. Thus, MoO₈ and RO₈ polyhedra are fully ordered in R₂MoO₆ compounds, which in fact can be considered as superstructures of fluorite (M₃O₆), containing 24 MO₂ fluorite units per unit cell, with unit-cell parameters related to that of cubic fluorite ( Å). A bond valence study demonstrates that the present crystal structure is especially stable for small rare-earth cations, and becomes more unstable when the R³⁺ size increases, thus explaining the observed preference of the large rare-earth molybdates for polymorphs β and γ with the same stoichiometry.     

Magnetic Behavior of R2Ba2CuPtO8 Oxides (R=Ho, Er, Tm, Yb, Lu, and Y)

Magnetic properties of polycrystalline R₂Ba₂CuPtO₈ (R=Ho, Er, Tm, Yb, Lu and Y) oxides have been studied from magnetization and magnetic susceptibility measurements. The lutetium and yttrium oxides behave as antiferromagnets and the estimated Néel temperatures are 5.2 and 5.7 K, respectively. In the case of the remaining R₂Ba₂CuPtO₈ oxides, Cu²⁺ and R³⁺ become antiferromagnetically ordered simultaneously, with the exception of TmBa₂CuPtO₈, where the χ vs T plot exhibits two maxima at 8 and 5 K, which have been assigned to the Néel temperatures of Cu²⁺ and Tm³⁺ sublattices, respectively. Taking into account the structure, a superexchange mechanism of the type R-O-Cu-O-R has been proposed in which the Cu²⁺ sublattice plays an important role as promoter of the antiferromagnetic interactions of ferromagnetically R³⁺ coupled in the a-c plane of the structure. Field-induced metamagnetic transitions have been observed below the Néel temperature in all cases; however, different critical fields are achieved depending on the nature of R³⁺ ions.     

Magnetic properties of Ln2−xLn′xCo17 compounds (Ln = Gd,Dy, Ho,or Er,Ln′ = Th or Ce)

Magnetic and structural characteristics of the ternary systems Ln_2?xTh_xCo₁₇ (Ln = Gd, Dy, Ho, and Er) and Ln_2?xCe_xCo₁₇ (Ln = Gd, Dy, and Ho) are presented. Incorporation of Th in the lattice stabilizes the Th₂Zn₁₇ structure, whereas incorporation of Ce does not; if the binary system has the Th₂Ni₁₇ structure the incorporation of Ce leaves the structure unchanged. The antiferromagnetic LnCo coupling observed in the Ln₂Co₁₇ systems persists in the ternary alloys. The moment of the cobalt sublattice is decreased when more than half of the Ln is replaced by Th, suggesting that the extra electron contributed by Th enters the Co d-band or d-shell. The direction of easy magnetization is in the basal plane for all composition in the Gd, Dy, and Ho systems. In Er_2?xTh_xCo₁₇ the easy direction is along the c-axis for x = 0 and 0.2, but is in the basal plane for higher thorium contents.     

Ferromagnetic exchange couplings showing a chemical trend in Cu-Ln-Cu complexes (Ln = Gd, Tb, Dy, Ho, Er)

Exchange couplings in isomorphous [LnCu(2)] were evaluated by high-frequency electron paramagnetic resonance and magnetization studies. The exchange parameter J(Ln-Cu) was decreased with an increase in the atomic number; J(Ln-Cu)/k(B) = 4.45(11), 2.27(6), 0.902(10), 0.334(3), and 0.136(8) K for Ln = Gd, Tb, Dy, Ho, and Er, respectively.     

Tuning of optical band gaps: syntheses, structures, magnetic properties, and optical properties of CsLnZnSe(3) (Ln = Sm, Tb, Dy, Ho, Er, Tm, Yb, and Y)

Eight new quaternary selenides CsSmZnSe(3), CsTbZnSe(3), CsDyZnSe(3), CsHoZnSe(3,) CsErZnSe(3), CsTmZnSe(3), CsYbZnSe(3), and CsYZnSe(3) have been synthesized with the use of high-temperature solid-state experimental methods. These compounds are isostructural with KZrCuS(3), crystallizing with four formula units in the orthorhombic space group Cmcm. The structure of these CsLnZnSe(3) compounds is composed of [LnZnSe(3)(-)] layers separated by Cs atoms. The Ln atom is octahedrally coordinated by six Se atoms, the Zn atom is tetrahedrally coordinated by four Se atoms, and the Cs atom is coordinated by a bicapped trigonal prism of eight Se atoms. Because there are no Se-Se bonds in the structure, the oxidation state of Cs is 1+, that of Ln is 3+, and that of Zn is 2+. CsYbZnSe(3) exhibits an antiferromagnetic transition at 11 K, whereas CsSmZnSe(3) does not follow a Curie-Weiss law. The remaining rare-earth compounds are paramagnetic, and the calculated effective magnetic moments of the rare-earth ions agree well with their theoretical values. Optical absorption data on face-indexed single crystals of CsSmZnSe(3), CsErZnSe(3), CsYbZnSe(3), and CsYZnSe(3) demonstrate that the optical band gap changes by more than 0.75 eV with the composition and by as much as 0.20 eV with the crystal orientation. The optical band gaps range from 2.63 eV (CsSmZnSe(3), CsErZnSe(3)) to 1.93 eV (CsYbZnSe(3)) for the (010) crystal face and 2.56 eV (CsErZnSe(3)) to 1.88 eV (CsYbZnSe(3)) for the (001) crystal face. The difference in the optical band gap of the (010) face vs the (001) face varies from +0.05 eV (CsYbZnSe(3)) to +0.20 eV (CsSmZnSe(3)).     

Preparation and properties of the MIIIU2O7.5 polyuranates (MIII = Y,Tb, Dy,Ho, Er,Tm, Yb,or Lu)

The novel compounds of the M^IIIU₂O_7.5 type (with M^III being yttrium or lanthanides from terbium to lutetium) have been prepared via hydrothermal synthesis from hydrated uranium(VI) oxide and aqueous solutions of M(III) nitrates at 200°C. Composition and structure of the products have been studied by means of elemental analysis, high-temperature X-ray diffraction, and IR spectroscopy; the products thermal stability has been estimated.     

Magnetic Properties of LnMnO3 (Ln=Ho, Er, Tm, Yb, and Lu)

Magnetic data are presented for LnMnO₃ (Ln=Ho, Er, Tm, Yb, and Lu) having the hexagonal crystal structure of P6₃cm. DC magnetization measurements show that magnetic order is not clearly observed for Ln=Ho-Yb, while an antiferromagnetic transition of the Mn³⁺ moments is found at ∼90 K for LuMnO₃, where the Lu³⁺ ion has no 4f localized moment. This is ascribed to both the paramagnetism of Ln³⁺ and the suppression of magnetization in the Mn³⁺ sublattices arising from strong antiferromagnetic interactions between Mn³⁺. Deviation from the Curie-Weiss law at low temperatures indicates the onset of antiferromagnetism. Some magnetization data of Ca-substituted compounds, Ln_0.5Ca_0.5MnO₃, which have the different crystal structure of orthorhombic Pnma, are also discussed briefly.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Fluoroplatinate(IV) der Lanthaniden LnF[PtF6]. (Ln = Pr,Sm, Gd,Tb, Dy,Ho, Er)

Fluoroplatinates(IV) of the Lanthanides LnF[PtF₆] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er) For the first time fluorides LnF[PtF₆] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er), all yellow have been obtained. From single crystal data they crystallize monoclinic, space group P2₁/n?C (No. 14), Z = 4, Pr: a = 1 125.77(19) pm, b = 559.04(7) pm, c = 910.27(17) pm, β = 107.29(1)°; Sm: a = 1 114.63(31) pm, b = 552.70(12) pm, c = 898.02(20) pm, β = 107.24(2)°; Gd: a = 1 112.12(15) pm, b = 551.22(7) pm, c = 891.99(11) pm, β = 107.09(1)°; Tb (Powder data): a = 1 108.88(20) pm, b = 552.71(9) pm, c = 889.56(16) pm, β = 107.30(1)°; Dy: a = 1 100.28(23) pm, b = 547.77(8) pm, c = 882.41(13) pm, β = 107.32(1); Ho: a = 1 099.11(16) pm, b = 546.16(7) pm, c = 879.45(15) pm, β = 107.34(1)°; Er: a = 1 095.10(16) pm, b = 544.82(10) pm, c = 874.85(14) pm, β = 107.37(1)°.     

Syntheses, structure, some band gaps, and electronic structures of CsLnZnTe3 (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Y)

Eleven new quaternary rare-earth tellurides, CsLnZnTe3 (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Y), were prepared from solid-state reactions at 1123 K. These isostructural materials crystallize in the layered KZrCuS3 structure type in the orthorhombic space group Cmcm. The structure is composed of LnTe6 octahedra and ZnTe4 tetrahedra that share edges to form [LnZnTe3] layers. These layers stack perpendicular to [010] and are separated by layers of face- and edge-sharing CsTe8 bicapped trigonal prisms. There are no Te-Te bonds in the structure of these CsLnZnTe3 compounds so the formal oxidation states of Cs/Ln/Zn/Te are 1+/3+/2+/2-. Optical band gaps of 2.13 eV for CsGdZnTe3 and 2.12 eV for CsTbZnTe3 were deduced from single-crystal optical absorption measurements. A first-principles calculation of the density of states and the frequency-dependent optical properties was performed on CsGdZnTe3. The calculated band gap of 2.1 eV is in good agreement with the experimental value. A quadratic fit for the lanthanide contraction of the Ln-Te distance is superior to a linear one if the closed-shell atom is included.     

Double dimethylammonium sulphates of Tb,Dy, Ho,Er, Tm,Yb, Lu and Y

Double sulphates of rare earths with dimethylammonium, with empirical formula (CH₃)₂NH₂Ln(SO₄)₂·4H₂O (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu and Y), were studied by means of thermogravimetry, derivative thermogravimetry and differential thermal analysis from 20 to 700°. Quantitative gravimetric analysis was used for the determination of rare earths and sulphate. The mechanism of thermal decomposition is also suggested.

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Zusammenfassung Doppelsulfate der seltenen Erden mit Dimethylammoniumionen der empirischen Formel (CH₃)₂NH₂Ln(SO₄)₂·4H₂O (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu und Y) wurden mittels TG, DTG und DTA im Temperaturbereich von 20–700° untersucht. Die Seltenen Erden und Sulfat wurden gravimetrisch bestimmt. Ein Mechanismus der thermischen Zersetzung wird vorgeschlagen.

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, 20–700° (₃)₂N₂Ln(S₄)₂·4₂, Ln=Tb, Dy, , Er, Tm, Yb, Lu Y. . .