ABSTRACT
Single crystals of Ca1-3x-yMnyâ¡xNd2x(MoO4)1-3x(WO4)3x molybdato-tungstates (â¡ denotes vacant sites) with a scheelite-type structure have been successfully grown by the Czochralski technique in an inert atmosphere. This paper presents the results of structural, optical, magnetic, and electrical properties, as well as the broadband dielectric spectroscopy measurements of single crystals with different Nd3+ ion concentrations, i.e., when x = 0.0050 or x = 0.0098, and with constant content of Mn2+ ions, i.e., when y = 0.0050. Our magnetic studies have shown that substitution of diamagnetic Ca2+ ions in the CaMoO4 matrix with paramagnetic Nd3+ ones with a content not exceeding 0.02 and having a screened 4f-shell revealed a significant effect of orbital diamagnetism and Van Vleck's paramagnetism. Both single crystals have revealed residual electrical conductivity without an intrinsic region and a change of sign of the Seebeck coefficient at ca. 230 K. Dielectric spectroscopy measurements have shown constant values of relative permittivity (εr â¼ 8) and loss tangent (tan δ â¼ 0.01) both up to 400 K and up to 1 MHz, as well as the Fermi energy (â¼0.04 eV) and the Fermi temperature (â¼500 K) determined for both crystals from the diffusion component of thermopower. These results suggest the presence of shallow acceptor and donor levels in the studied crystals.
ABSTRACT
Microcrystalline samples of CoRE2W2O10 tungstates (RE = Y, Dy, Ho, Er) were prepared by a high-temperature solid-state reaction and then sintered into a ceramic form for unique properties and potential applications. For this purpose, structural, microscopic, ultraviolet-visible (UV-vis), magnetic, electrical, and thermoelectric measurements were performed. These studies showed a monoclinic structure, paramagnetism, short-range antiferromagnetic interactions in all samples, long-range ferrimagnetic interactions only in CoY2W2O10, poor n-type conductivity of 6.7 × 10-7 S/m at room temperature, strong thermal activation (Ea1 = 0.7 eV) in the intrinsic region, a strong increase in the power factor (S2σ) above 300 K, a Fermi energy (EF) of 0.16 eV, and a Fermi temperature (TF) of 1800 K. The above studies suggest that anion vacancy levels, which act as doubly charged donors, and to a lesser extent, the mixed valence band of cobalt ions (Co2+, Co3+), which are located below the bottom of the conduction band and below the Fermi level, are responsible for electron transport.
ABSTRACT
Single crystals of Pb1-3xâ¯xNd2x(MoO4)1-3x(WO4)3x (PNMWO) with scheelite-type structure, where ⯠denotes cationic vacancies, have been successfully grown by the Czochralski method in air and under 1 MPa. This paper presents the results of structural, optical, magnetic and electrical, as well as the broadband dielectric spectroscopy measurements of PNMWO single crystals. Research has shown that replacing diamagnetic Pb2+ ions with paramagnetic Nd3+ ones, with a content not exceeding 0.01 and possessing a screened 4f-shell, revealed a significant effect of orbital diamagnetism and Van Vleck's paramagnetism, n-type electrical conductivity with an activation energy of 0.7 eV in the intrinsic area, a strong increase of the power factor above room temperature for a crystal with x = 0.005, constant dielectric value (~30) and loss tangent (~0.01) up to room temperature. The Fermi energy (~0.04 eV) and the Fermi temperature (~500 K) determined from the diffusion component of thermopower showed shallow donor levels.
ABSTRACT
New Gd3+- and Mn2+-co-doped calcium molybdato-tungstates with the chemical formula of Ca1−3x−yMnyâ¯xGd2x(MoO4)1−3x(WO4)3x (labeled later as CaMnGdMoWO), where ⯠denotes vacant sites in the crystal lattice, 0 < x ≤ 0.2500 and y = 0.0200 as well as 0 < y ≤ 0.0667 and x = 0.1667 were successfully synthesized by high-temperature solid-state reaction method and combustion route. Obtained ceramic materials crystallize in scheelite-type structure with space group I41/a. Morphological features and grain sizes of powders under study were investigated by SEM technique. Spectroscopic studies within the UV-vis spectral range were carried out to estimate the direct band gap (Eg) and Urbach energy (EU) of obtained powders. EPR studies confirmed the existence of two types of magnetic objects, i.e., Mn2+ and Gd3+ ions, and significant antiferromagnetic (AFM) interactions among them.
Subject(s)
Magnetic Phenomena , Magnetics , X-Ray Diffraction , Powders , CeramicsABSTRACT
A series of Co2+-doped and Gd3+-co-doped calcium molybdato-tungstates, i.e., Ca1-3x-yCoyxGd2x(MoO4)1-3x(WO4)3x (CCGMWO), where 0 < x ≤ 0.2, y = 0.02 and represents vacancy, were successfully synthesized by high-temperature solid-state reaction method. XRD studies and diffuse reflectance UV-vis spectral analysis confirmed the formation of single, tetragonal scheelite-type phases with space group I41/a and a direct optical band gap above 3.5 eV. Magnetic and electrical measurements showed insulating behavior with n-type residual electrical conductivity, an almost perfect paramagnetic state with weak short-range ferromagnetic interactions, as well as an increase of spin contribution to the magnetic moment and an increase in the power factor with increasing gadolinium ions in the sample. Broadband dielectric spectroscopy measurements and dielectric analysis in the frequency representation showed a relatively high value of dielectric permittivity at low frequencies, characteristic of a space charge polarization and small values of both permittivity and loss tangent at higher frequencies.
