• Bulletin of the Korean Chemical Society
• /
• v.24 no.6
• /
• pp.739-743
• /
• 2003

New quaternary compounds $ANb_2PS_{10}$ (A = Na, Ag) and $AuNb_4P_2S_{20}$ were synthesized and characterized. The structures of three compounds consist of one-dimensional infinite chains built by [$Nb_2S_{12}$] and [$PS_4$] units. Cation atoms are occupied within the van der Waals gap of sulfur atoms between infinite chains to make -S…$M^+$…S- contacts. There is only one Au atom site and so crystallographically a unit cell contains four equivalent Au atoms in $AuNb_4P_2S_{20}$. This is only the half of the numbers of Na or Ag atoms in $NaNb_2PS_{10}$ or $AgNb_2PS_{10}$. The ratio between $Nb_2PS_{10}$ matrix vs the cation is, therefore, 1 : 1 for Ag and Na, but it is 2 : 1 for Au. Mixed valency in Au or Nb was expected to balance the charge in the latter compound. The electronic structures calculated based on the extended Huckel tight-binding method show that $ANb_2PS_{10}$ (A = Ag, Na) are semiconducting, while $AuNb_4P_2S_{20}$ is metallic, which is not consistent with the experimental results of these three compounds that all exhibit semiconducting property. The result of calculation suggests that $AuNb_4P_2S_{20}$ might be a magnetic insulator. Magnetic measurement experiment exactly proved that the compound is a Slater antiferromagnetic material with the Neels' temperature of 45 K. It is recognized, therefore, that electronic structure analysis is very useful to understand the properties of compounds.

• Journal of the Korean Chemical Society
• /
• v.35 no.2
• /
• pp.99-104
• /
• 1991

Nonstoichiometric solid solutions of Sr$_{1+x}Er _{1-x} FeO _{4-y}$ system (x = 0.00, 0.25, 0.50, 0.75 and 1.00) with layered $K_2NiF_4$ type structure were prepared at 1350$^{\circ}$C under atmospheric pressure. By the analysis of X-ray diffraction, the crystallographic structures of the solid solution of all compositions were found to be pseudo-tetragonal system. Nonstoichiometric chemical formulas have been determined by Mohr salt analysis. It shows that the amount of Fe$^{4+}$ increases with increasing x up to 0.50 and then decreases, and the value of oxygen nonstoichiometry increases with increasing x value. Mixed valency states of Fe$^{3+}$ and Fe$^{4+}$ in the sample were identified again by Mossbauer spectroscopic analysis at 298 K. Electrical conductivity varied within the semiconductivity range of 10-2 ∼ 10-7(${\Omega}$-1cm-1), activation energy for electrical conduction decreased with the increment of the mole ratio of Fe$^{4+}$ or ${\tau}$ value. The conduction mechanism could be explained by the hopping model of the conduction electrons between the valency states of Fe$^{3+}$ and Fe$^{4+}$.

• Transactions on Electrical and Electronic Materials
• /
• v.18 no.6
• /
• pp.311-315
• /
• 2017

The perovskite system $(Ba^{2+}{_{1-x}}La^{3+}{_x})Fe^{3+}{_{1-t}}Fe^{4+}{_t}O_{3-y}$ (y = (1 - x --t)/2) having a composition of x = 0.0, 0.1, 0.2, and 0.3 showedean increase in $Fe^{4+}$ mole ratios with an increase in oxygen partial pressure ($N_2{\rightarrow}air{\rightarrow}O_2$), and with an increasefin s, the $Fe^{3+}$ quantity decreased and oxygen content (3-y value) increased. For each N sampls heat-treated in $N_2$ gas, a considerable weight gain, i.e.g a steadynincrease if oxygen content, was observed in the TGA data on the cooling process. The conductivity values at a constant temperature were in the order of $N_2$$O_2$; the respective log ${\sigma}$ values (${\Omega}^{-1}{\cdot}cm^{-1}$) at 323 K of the BL0 sample were -5.75 (BL0-N), -3.39 (BL0-A), and -0.53 (BL0-O). The mixed valencies of $Fe^{3+}$ and $Fe^{4+}$ ions in each sample were also confirmed by both the oxidation curve above 350 mV and the cathodic reduction curve below 200 mV from cyclic voltammetry.

• Journal of the Korean Chemical Society
• /
• v.38 no.12
• /
• pp.873-879
• /
• 1994

A series of samples of solid solutions in the $Sr_xEu_{1-x}FeO_{3-y}(0.00{\leq}x{\leq}1.00)$ system has been prepared at $1200^{\circ}C$ under an atmospheric air pressure. The structures of solid solutions are studied by X-ray diffraction, thermal, Mohr salt, and Mossbauer spectroscopic analyses. Their physical properties are also discussed with the electrical conductivities. X-ray diffraction data for the compositions of x = 0.00, 0.25, and 1.00 are assigned to the orthorhombic and the compositions of x = 0.50 and 0.75 to the cubic systems. The lattice volume reduced to cubic cell increases with the x value. The mole ratio of $Fe^{4+}$ iometric chemical formulas of the system are formulated from the x, $\tau$, and y values. The mixed valency state of Fe ions, the oxygen coordination, and covalent bond character are discussed with the Mossbauer spectroscopic data. The activation enegy of the electrical conductivities depends on the $\tau$ value in the temperature range of -$100^{\circ}C$ to $600\circC$ under the air pressure. The Mossbauer spectrum and electrical conductivity of the solid solutions are discussed with nonstoichiometric chemical compositions.

• Journal of the Korean Chemical Society
• /
• v.32 no.1
• /
• pp.3-8
• /
• 1988

Nonstoichiometric solid solutions of the $Sr_{1+x}Dy_{1-x}FeO_{4-y}$ system (x = 0. 00, 0. 25, 0. 50, 0. 75 and 1. 00) with layered $K-2NiF_4$ type structure were prepared at 1200$^{\circ}$C under atmospheric pressure. X-ray powder diffraction spectra show that the crystallographic phases of the samples are tetragonal within the x range. Nonstoichiometric chemical formulas have been determined by Mohr salt analysis and it shows that the amount of $Fe^{4+}$ ion or ${\tau}$ value increases with increasing x. Electrical conductivities of the samples which were measured in the temperature range of $-100{\sim}200^{\circ}$C under atmospheric air pressure are varied within the semiconductivity range of $l0^{-8}{\sim}10^{-2}(ohm^{-1}{\cdot}cm^{-1}$) and the activation energies are also varied from 0.02 to 0.08 eV. Mixed valency state of $Fe^{3+}$ and $Fe^{4+}$ in the sample of $Sr_{1.00}Dy_{1.00}FeO_{4.04}$ was identified again by Mossbauer spectrum at 200K.

• Journal of the Korean Chemical Society
• /
• v.32 no.1
• /
• pp.9-14
• /
• 1988

Perovskite type compounds of the $La_{1-x}Ca_xFeO_{3-y}$ system were prepared from stoichiometric mixtures of La_2O_3,\;CaCO_3$, and Fe(NO-3)_3{\cdot}9H_2O$ by heating at 1100$^{\circ}C$ for 24 hours. The crystallographic structures of the solid solutions of all compositions were orthorhombic systems. X-ray diffraction and Mohr salt analysis revealed that at higher y value the phase transition due to vacancy ordering occured and that the lattice volume decreased when the x value was increased. The value of nonstoichiometric ratio y were found to be in the range of $0.0{\sim}0.5$. Electrical conductivities of this systems are measured in temperature range of -100 to 100$^{\circ}C$. Ionic contribution to total conductivity was found from activation energy in the phase containing the open pathway due to vacancy ordering.

• Journal of the Korean Chemical Society
• /
• v.35 no.6
• /
• pp.617-624
• /
• 1991

Nonstoichiometric solid solutions of $Y_{1-x}A_xFeO_{3-y}$ (A = Ca, Sr) systems with perovskite structure were prepared for x = 0.00, 0.25, 0.50, 0.75 and 1.00 at 1200$^{\circ}C$ under atmospheric pressure, respectively. Crystallographic structures of the solid solutions of all compositions have been determined by the analysis of X-ray diffraction patterns. Reduced lattice volume of the $Y_{1-x}Ca_xFeO_{3-y}$ system was decreased with increasing x value and that of the $Y_{1-x}Sr_xFeO_{3-y}$ system was increased with increasing the x value. The mole ratios of $ Fe^{4+}$ to $ Fe^{3+}$, ${\tau}$, values in the solid solutions have been determined by Mohr salt's method of analysis and then the mixed valency was identified by Mossbauer spectroscopic analysis at 298 K. The y values were calculated from the x and ${\tau}$, and then nonstoichiometric chemical formulas were fixed. The conduction mechanism could be explained by hopping model of the conduction electrons between the mixed valence states.