• Bulletin of the Korean Chemical Society
• /
• 제10권3호
• /
• pp.234-238
• /
• 1989

The crystal structure of partially $Ag^+$-exchanged zeolite A, $Ag_{3.2}Na_{8.8}$-A, vacuum dehydrated at $360^{\circ}C$ and then exposed to 0.1 torr of cesium vapor for 12 hours at $250^{\circ}C$ has been determined by single-crystal X-ray diffraction techniques in the cubic space group Pm3m (a = 12.262(2)${\AA})\;at\;21(1)^{\circ}C$. The structure was refined to the final error indexes $R_1=0.068\;and\;R_2=0.072$ by using 338 reflections for which $I_o\;>\;3{\sigma}(I_o)$ and the composition of unit cell is $Ag_{3.2}Cs_{8.8}-A.\;3\;Cs^+$ ions lie on the centers of the 8-rings at sites of D4h symmetry. Two crystallographycally different 6-ring $Cs^+$ ions were found: 1.5 $Cs^+$ ions at Cs(2) are located inside of sodalite cavity and 4.3 $Cs^+$ ions at Cs(3) are located in the large cavity. The fractional occupancies observed at Cs(2) and Cs(3) indicate that the existence of at least three types of unit cells with regard to the 6-ring $Cs^+$ ions. For example, 50% of unit cells may have two $Cs^+$ ions at Cs(2) and 4 $Cs^+$ ions at Cs(3). 30% of unit cells may have one Cs+ ion at Cs(2) and 5 $Cs^+$ ions at Cs(3). The remaining 20% would have one $Cs^+$ ion at Cs(2) and 4 $Cs^+$ ions at Cs(3). On threefold axes of the unit cell two non-equivalent Ag atom positions are found in the large cavity, each containing 0.64 and 1.92 Ag atoms, respectively. A crystallographic analysis may be interpreted to indicate that 0.64 $(Ag_5)^+$ clusters are present in each large cavity. This cluster may be viewed as a tetrasilver molecule $(Ag_4)^0$(bond length, 2.84${\AA}$) stabilized by the coordination of one $Ag^+$ ion.

• JSTS:Journal of Semiconductor Technology and Science
• /
• 제7권1호
• /
• pp.56-65
• /
• 2007

This paper describes physical meanings of various influences of cavity (or pillar) shape and filling factor of dielectric material on band structures in two-dimensional photonic crystals. Influences of circular and rectangular cross-sections of cavity (or pillar) arrays on photonic band structures are considered theoretically, and significant aspects of square and triangular lattices are compared. It is shown that both averaged dielectric constant of the photonic crystal and distribution profile of photon energy play important roles in designing optical properties. For the triangular lattice, especially, it is shown that cavity array with a rectangular cross-section breaks the band structure symmetry. So, we discuss this point from the band structure and address optical properties of lattice with a circular cross-section cavity.

• 한국전기전자재료학회논문지
• /
• 제16권4호
• /
• pp.272-279
• /
• 2003

In this work Zn$_4$GeSe$_{6}$ :CO$^{2+}$ single crystals were grown by the chemical transport reaction method in which the iodine was used as the transporting agent. The Zn$_4$GeSe$_{6}$ :CO$^{2+}$ single crystal was found to have a monoclinic structure. The optical absorption spectra of grown crystals were investigated using a temperature-controlled UV-VIS -NIR spectrophotometer. The temperature dependence of band-edge absorption was in a good agreement with the Varshni equation. The observed impurity absorption peaks could be explained as arising from the electron transition between energy levels of Co$^{2+}$ ion sited at the T$_{d}$ symmetry point.

• 한국지구과학회지
• /
• 제18권6호
• /
• pp.553-558
• /
• 1997

등축정계의 결정구조를 지니는 무색 투명한 저코니아($Zr_{0.73}Y_{0.27}O_{1.87}$) 결정을 $Y_2O_3$를 안정제로 사용하여 Bridgman-Stockbager법(또는 Skull 용융법)으로 합성하였다. 육성된 결정은 유리광택을 나타내며 동시에 약간의 지방 광택도 띤다. 저코니아 결정은 편광현미경하에서 등방성을 나타내며 이방성의 징후는 발견되지 않는다. 모스 경도는 $8{\sim}8\frac{1}{2}$이고 비중은 5.85이다. 자외선하에서는 약한 백색 형광을 낸다. 단결정법으로 결정한 저코니아의 결정구조는 등축정계이며, 공간군은 $Fm3m({O^5}_h)$이다. 단위포 상수(a)는 $5.1552(5){\AA}$이며, $V=136.99(5){\AA}$, Z=4, R=0.0488이다. 저코니움 원자는 각 모서리에 산소 원자가 자리잡고 있는 육면체의 중심에 위치하고 있으며, 각 산소 원자는 저코니움 원자로 되어 있는 사면체의 중심에 위치하고 있다. 결국 8:4의 배위수가 성립하는 구조를 하고 있다.

• Bulletin of the Korean Chemical Society
• /
• 제22권7호
• /
• pp.703-708
• /
• 2001

K2NiF4-type organic-based perovskites of the (C4H9NH3)2FexPb1-xCl4 (x=0.00, 0.25, 0.50, and 0.75) system have been synthesized using a low-temperatu re solution method under a flowing argon gas. When stoichiometric butylamine, iron chloride, and lead chloride are mixed, a yellow solution are obtained from slow cooling of 90 to -10 $^{\circ}C.$ The final product is a plate-like yellow crystal. The X-ray crystallographic analysis has been carried out using XRD in the range of $5^{\circ}{\leq}$ 2${\theta}$ ${\leq}80^{\circ}.$ The local symmetry around the absorbing Pb atom of the samples has been determined by the EXAFS spectroscopic study. The crystals assign to orthorhombic system by the XRD analysis. The FT-IR spectra are analyzed in the range of 600 to 3300 cm-1 . DSC and TGA are measured to detect thermal stability between 30 and 300 $^{\circ}C.$ Two endothermic peaks are detected in all samples. The electrical conductivity has been measured using the four-probes technique for the (C4H9NH3)2FexPb1-xCl4 system in 300-460 K. Photoluminescence phenomenon was also investigated at room-temperature.

• 한국결정학회지
• /
• 제1권2호
• /
• pp.84-90
• /
• 1990

1,3-Diazatricyclo (5.2.1.O5.10) decade-2,4dione, C8H10N2O2의 단위세포 상수는a=6.585(7), b=9.089(4), c=12.937(10)A, β=95.72(5)˚, V=770.43, Dc=1.4391c0, 1=1.Ocm-1,7 =295 ˚K, 공간군은 P21/n이고 단사 정계이며 Z =4이 다. λ(Mo K u ) =0.7093A을 사용한 698개 의 회절 반점에 대한 최종 신뢰도 R값은 0.037이다. 본 화합물은 N1-(w-butenyl)uracil의 분자내 (2+2) 광고리화 반응 생성물이며, (5.1. 2.O5.10) tricyclic 계에 속한다. Inversion symmetry에 의해 관련된 한 쌍의 분자들은 uracil 부분의 02와H3간 의 강한 수소 결합을 하고있다

• The Korean Journal of Ceramics
• /
• 제5권4호
• /
• pp.341-347
• /
• 1999

An ambiguity on the correct room temperature structure of $Bi_5Ti_3FeO_{15}$ was resolved using a combined Rietveld refinement of neutron and X-ray diffraction. The structure of this compound has been reported to have a space group of F2mm (adopting 2-fold rotation symmetry along the c-axis) or A21am. However, our diffraction, study reveals that some reflections would violate F-centering and confirm that the belong to $A2_1$am. Out refinement with the space group of $A2_1$am converged at $R_p=6.85%, R_wp=9.23%$ and $\chi^2$=1.66 for an isotropic temperature model with 85 variables. The lattice constants are a=5.4677(1) $\AA$, b=5.4396(1) $\AA$, and c=41.2475(8)$\AA$. In structure, Ti/Fe atoms at the oxygen octahedral sites of the perovskite unit are completely disordered, resulting in that these atoms are transparent in neutron diffraction. The octahedra of the perovskite unit are relatively displaced along the a-axis against the Bi atoms, which contribute as a major component to the spontaneous polarization of $Bi_5Ti_3FeO_{15}$.

• 한국자기학회:학술대회 개요집
• /
• 한국자기학회 2011년도 임시총회 및 하계학술연구발표회
• /
• pp.7-8
• /
• 2011

Basically, the lattice mismatch between film and substrate can make those BiFeO3(BFO) films distorted with strain structure. BFO phase can be stabilized on LaAlO3(LAO) represents the example of a multiferroic with giant axial ratio. Its crystal structure is not strictly tetragonal, but tetragonal with a slight monoclinic distortion and related to the rotation of the oxygen octahedra. In this study, we show that phases with a tetragonal-like epitaxial BFO films can indeed be ferroelectric and also can be stabilized via epitaxial growth onto LAO. Recent reports on epitaxial BFO films show that the crystal structure changes from nearly rhombohedral ("R-like") to nearly tetragonal("T-like") at strains exceeding approximately -4.5%, with the "T-like" structure being characterized by a highly enhanced c/a ratio. While both the "R-like" and the "T-like" phases are monoclinic, our detailed x-ray diffraction results reveal asymmetry change from MA and MC type, respectively. By applying additional strain or by modifying the unit cell volume of the film by substituting Ba for Bi, the monoclinic distortion in the "T-like" MC phase is reduced, i.e. the system approaches a true tetragonal symmetry. There are two different M-H loops for $Bi_{1-x}Ba_xFeO_{3-{\delta}}$(BBFO) and BFO films on SrTiO3(STO) & LAO substrates. Along with the ferroelectric characterization, these magnetic data indicate that the BFO phase stabilized on LAO represents the first example of a multiferroic with giant axial ratio. However, there is a significant difference between this phase and other predicted ferroelectrics with a giant axial ratio: its crystal structure is not strictly tetragonal, but tetragonal with a slight monoclinic distortion. Therefore, in going from bulk to highly-strained films, a phase sequence of rhombohedral(R)-to-monoclinic ["R-like" MA-to-monoclinic, "T-like" MC-to-tetragonal (T)] is observed. This sequence is otherwise seen only near morphotropic phase boundaries in lead-based solid-solution perovskites (i.e. near a compositionally induced phase instability), where it can be controlled by electric field, temperature, or composition. Our results show that this evolution can occur in a lead-free, stoichiometric material and can be induced by stress alone. Those major results are summarized as follows ; 1) Ba-doping increases the unit cell volume, 2) BBFO on LAO can be fully strained up to x=0.08 as a strain limit (Fig. 1), 3) P(E) & M(H) properties can be tuned by the variation of composition, strain, and film thickness.

• Bulletin of the Korean Chemical Society
• /
• 제5권3호
• /
• pp.117-121
• /
• 1984

The structure of $CS_{7.3}Ag_{4.7}Si_{12}Al_{12}O_{48}$, vacuum dehydrated zeolite A with all Na+ ions replaced by $Cs^+$ and $Ag^+$ as indicated, has been determined by single-crystal x-ray diffraction techniques in the cubic space group, Pm3m (a = 12.282 (1) ${\AA}$). The structure was refined to the final error indices $R_1$$R_2$ (weighted) = 0.099 using 347 independent reflections for whind intlch $I_0\;>\;3{\sigma}(I_0)$. Although deydration occurred at $360^{\circ}C$, no silver atoms or clusters have been observed. The 8-ring sites are occupied only by $Cs^+$ ion, and the 4-ring sites only by a single $Ag^+$ ion. The 6-ring sites contain $Ag^+$ and $Cs^+$ ions with $Ag^+$ nearly in 6-ring planes and $Cs^+$ well off them, one on the sodalite unit side. With regard to the 6-rings, the structure can be represented as a superposition of two types of unit cells: about 70 % have $4Ag^+$ and $4Cs^+$ ions, and the remaining 30 % have $3Ag^+$ and $5Cs^+$. In all unit cells, $3Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry; these ions are approximately 0.3 ${\AA}$ further from their nearest framework-oxygen neighbors than the sum of the appropriate ionic radii would indicate. To minimize electrostatic repulsions, the $Cs^+$ ions at Cs(1) are not likely to occupy adjacent 6-rings in the large cavity; they are likely to be tetrahedrally arranged when there are 4.

• Bulletin of the Korean Chemical Society
• /
• 제26권7호
• /
• pp.1090-1096
• /
• 2005

$Ag_4Br_4$ nanoclusters have been synthesized in about 75% of the sodalite cavities of fully $K^+$-exchanged zeolite A (LTA). An additional KBr molecule is retained in each large cavity as part of a near square-planar $K_4Br^{3+}$ cation. A single crystal of $Ag_{12}$-A, prepared by the dynamic ion-exchange of $Na_{12}$-A with aqueous 0.05 M $AgNO_3$ and washed with $CH_3OH$, was placed in a stream of flowing 0.05 M KBr in $CH_3OH$ for two days. The crystal structure of the product ($K_9(K_4Br)Si_{12}Al_{12}O_{48}{\cdot}0.75Ag_4Br_4$, a = 12.186(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm m. It was refined with all measured reflections to the final error index $R_1$ = 0.080 for the 99 reflections for which $F_o\;{\gt}\;4_{\sigma}\;(F_o)$. The thirteen $K^+$ ions per unit cell are found at three crystallographically distinct positions: eight $K^+$ ions in the large cavity fill the six-ring site, three $K^+$ ions fill the eight-rings, and two $K^+$ ions are opposite four-rings in the large cavity. One bromide ion per unit cell lies opposite a four-ring in the large cavity, held there by two eight-ring and two six-ring $K^+$ ions ($K_4Br^{3+}$). Three $Ag^+$ and three $Br^-$ions per unit cell are found on 3-fold axes in the sodalite unit, indicating the formation of nano-sized $Ag_4Br_4$ clusters (interpenetrating tetrahedra; symmetry $T_d$; diameter ca. 7.9 $\AA$) in 75% of the sodalite units. Each cluster (Ag-Br = 2.93(3) $\AA$) is held in place by the coordination of its four $Ag^+$ ions to the zeolite framework (each $Ag^+$ cation is 2.52(3) $\AA$ from three six-ring oxygens) and by the coordination of its four $Br^-$ ions to $K^+$ ions through six-rings (Br-K = 3.00(4) $\AA$).