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Zeolites were synthesized from paper-sludge ash in different alkali solutions. The ash used in this study has a high-Ca content and a low abundance of Si, in part due to the presence of calcite that is used as a paper filler. The major minerals present in the ash are gehlenite (Ca 2 Al 2 SiO 7 ) and anorthite (CaAl 2 Si 2 O 8 ). Three kinds of alkali solutions (NaOH, KOH, and LiOH) at four different concentrations (1, 2, 3, and 4 M ) were reacted with paper-sludge ash at 90 °C for 24 h. Powder X-ray diffraction showed that hydroxysodalite (Na 6 Al 6 Si 6 O 24 ·8H 2 O) and zeolite Linde F (KAlSiO 4 ·1.5H 2 O) had formed in NaOH and KOH solutions, respectively, and that anorthite had dissolved in these alkaline solutions, whereas gehlenite had remained unaffected. In the LiOH solution, both anorthite and gehlenite dissolved, and various minerals, including Li-ABW zeolite (Li 4 Al 6 Si 6 O 16 ·4H 2 O), hydrocalumite [Ca 2 Al(OH) 6 (Cl, OH)·3H 2 O], tobermorite [Ca 5 Si 6 O 16 (OH) 2 ·4H 2 O], katoite [Ca 3 Al 2 (SiO 4 )(OH) 8 ], and portlandite [Ca(OH) 2 ] formed. The products of mineral synthesis from paper-sludge ash by reaction in alkaline solutions strongly depend on the specific alkali present.

In synthetic single crystals of the olivine group, a strong compositional zoning along the growth direction has often been observed. Here we have synthesized large homogeneous single crystals of forsterite doped with manganese (50 mm×150–200 mm) by the Czochralski method using a large volume crucible, at ∼1950 °C in an N 2 atmosphere. The size of the crystals in this study is the largest reported. The homogeneous parts of as-grown crystals with the compositions of (Mn 0.004 Mg 0.996 ) 2 SiO 4 and (Mn 0.011 Mg 0.989 ) 2 SiO 4 are as large as 20×20×50 mm 3 [ x =0.0040±0.0004 in (Mn x Mg 1− x ) 2 SiO 4 ] and 12×12×30 mm 3 [ x =0.011±0.001], respectively. The crystals were prepared to allow for accurate measurements of physical properties and their anisotropies of pure Mn bearing forsterite, to extract the effect of Mn itself, ultimately for the study of the Earth's mantle. The polarized absorption spectra were measured for an evidence of measured anisotropy, and the clear pleochroism was observed.

A new superstructure was found in mordenite (Na 5.59 Ca 1.80 Al 9.19 Si 38.81 O 96 ·nH 2 O) from Challis Valley, Idaho—a zeolite widely used in previous studies. The occurrence of the superstructure reflections were observed in 12 specimens from two rock samples, at the midpoint of layers in the oscillation photographs around the a * and b * axes, but not around the c * axis. The apparent 2 a , 2 b , and c axes are orthogonal. In spite of yielding an apparent orthorhombic cell, careful observation of the intensities revealed that the superstructure is monoclinic with twice the volume of the orthorhombic cell: a ′ = 27.356(9), b ′ = 27.356(9), c ′ = 7.517(2) A, γ′ = 97.14(4)°, and V ′ = 5582(4) A 3 . The presence of the superstructure was examined for specimens from ten other localities and a synthetic sample but there was no evidence for extra spots of the superstructure, indicating that the occurrence is not common. The large displacement factors of O8 oxygen, and its associated 180° T-O-T angle that is energetically unfavorable, are basic to the mordenite structure. In the monoclinic superstructure the O8 oxygen is decomposed into several asymmetric O atoms by the symmetry reduction. The large displacement smearing of O8 oxygen perpendicular to the straight T-O-T, are explained by the superposition of decomposed O atoms. The extra spots are predominantly observed in the reciprocal planes with l = odd in the same way as diffuse streaks. The observation of extra spots and diffuse streaks suggests that there are three kinds of domains in the mordenite, one in the ordered form and two others in the random form of c /2 linear displacements. The domain in the ordered form represents the superstructure. Thus, we propose a model for the superstructure in which the c /2 displacement occurs alternatively in the two basic unit cells slightly modified in the superstructure, yielding the periodic arrangements.

To ensure the presence of coesite and its transformed polymorph, quartz, in ultrahigh-pressure (UHP) rocks and to examine the relic of the phase transformation, crystal structures were analyzed by single-crystal X-ray diffraction (XRD) directly using the rock thin section mounted on a slide glass. The rock sample used is a coesite-bearing eclogite from the Sulu UHP terrain, eastern China. The crystal structures were determined successfully by this new method and the presence of coesite and quartz in UHP rocks was identified for the first time by XRD. The R -factor [ R ( F )] converged to 0.046 for coesite and 0.087 for quartz. The displacement ellipsoids for coesite and quartz are larger than those previously reported for these two phases, which is consistent with expected effects of trapped strain due to the phase transformation from coesite to quartz during exhumation from the Earth’s mantle. This paper is the first report of single-crystal XRD of a rock thin section on a glass slide and establishes the technique, and provides proof-of-concept of the method. Although the mineral species included in a thin section can often be identified by other methods, such as Raman spectroscopy, an advantage of the reported method is that it can be applied to any mineral in a thin section, and not just to the UHP minerals. Moreover, it is applicable to an unknown or new mineral in a thin section, discarding the spots of known minerals and constructing a lattice from the residual spots to find the structure of the unknown phase.

Crystal structure of Li2(EMIm)(N(SO2CF3)2)3 (EMIm = 1-ethyl-3-methylimidazolium cation) has been determined by single-crystal X-ray diffraction as a structural clue of ionic liquid electrolytes for lithium batteries. Li2(EMIm)(N(SO2CF3)2)3 crystallizes in the space group P 2 1 / c , a = 15.184 ( 3 ) A , b = 11.358 ( 3 ) A , c = 21.249 ( 5 ) A , β = 111.454 ( 12 ) ° , Z = 4 , V = 3561.18 ( 14 ) A 3 . Two of the three N(SO2CF3)2 anions have cis-conformations and the third anion shows a trans-conformation. The asymmetric unit contains two crystallographically independent lithium ions and both of them are trigonal-bipyramidally coordinated by five oxygen atoms of N(SO2CF3)2 anions, forming a two-dimensional network. EMIm cation occupies a space in the network, weakly interacting with the anions.

Paper sludge ash was partially converted into zeolites by reaction with 3M NaOH solution at 90 degrees C for 24 h. The paper sludge ash had a low abundance of Si and significant Ca content, due to the presence of calcite that was used as a paper filler. Diatomite was added to the NaOH solution to increase its Si content in order to synthesize zeolites with high cation exchange capacity. Diatomite residue was filtered from solution before addition of ash. The original ash without addition of diatomite yielded hydroxysodalite with a cation exchange capacity ca. 50 cmol/kg. Addition of Si to the solution yielded Na-P1 (zeolite-P) with a higher cation exchange capacity (ca. 130 cmol/kg). The observed concentrations of Si and Al in the solution during the reaction explain the crystallization of these two phases. The reaction products were tested for their capacity for PO(4)(3-) removal from solution as a function of Ca(2+) content, suggesting the formation of an insoluble Ca-phosphate salt. The product with Na-P1 exhibits the ability to remove NH(4)(+) as well as PO(4)(3-) from solution in concentrations sufficient for application in water purification. Both NH(4)(+) and PO(4)(3-) removal showed little variation with pH between 5 and 9. Alternative processing methods of zeolite synthesis, including the addition of ash to an unfiltered Si-NaOH solution and addition of a dry ash/diatomite mixture to NaOH solution, were tested. The third process yielded materials with lower cation exchange capacity due to formation of hydroxysodalite. The second process results in a product with relatively high cation exchange capacity, and reduces the number of processing steps necessary for zeolite synthesis.

(2006). Sakura Ishi (Cherry Blossom Stones): Mica Pseudomorphs of Complex Cordierite-Indialite Intergrowths from Kameoka, Kyoto Prefecture, Japan. Rocks & Minerals: Vol. 81, No. 4, pp. 284-292.

Racemic samples of chiral five-membered cyclic nitroxides, 2,2,5,5-tetrasubstituted pyrrolidine-1-oxyls bearing one or two 4-hydroxyphenyl groups on the stereogenic centers [C(2) or C(2) & C(5)] adjacent to the NO radical moiety, exist as a racemic conglomerate in the crystalline state, whereas those having one or two 3-hydroxyphenyl groups at the same positions belong to a racemic compound. The key intermolecular interactions in controlling whether these racemates crystallize in a homochiral way or a heterochiral manner have been investigated by X-ray crystallographic analysis and magnetic susceptibility measurements.

We synthesized a single crystal of the MgO–SiO 2 system, forsterite, as large as 3500 carats. The quality of a large single crystal depends on the purity of the starting reagents and the stoichiometry of the initial mixture. Here we used high-purity (99.99 wt%) granular MgO and SiO 2 specimens of ∼2 mm size, as starting materials. Reagents of this grain size are easy to handle, and are suited for obtaining a large amount (above 1 kg) of a complete stoichiometric mixture. We are capable of producing large homogeneous single crystals over 50 mm diameter and 150 mm length.

Fluoroacid–base reactions of a room-temperature ionic liquid, 1-ethyl-3-methylimidazolium fluorohydrogenate (EMIm(HF)2.3F, EMIm = 1-ethyl-3-methylimidazolium cation), and Lewis fluoroacids (BF3, PF5, AsF5, NbF5, TaF5 and WF6) give EMIm salts of the corresponding fluorocomplex anions, EMImBF4, EMImPF6, EMImAsF6, EMImNbF6, EMImTaF6 and EMImWF7, respectively. Attempts to prepare EMImVF6 by both the acid–base reaction of EMIm(HF)2.3F with VF5 and the metathesis of EMImCl with KVF6 failed due to the strong oxidizing power of the pentavalent vanadium, whereas EMImSbF6 was successfully prepared only by the metathesis of EMImCl and KSbF6. EMImBF4, EMImSbF6, EMImNbF6, EMImTaF6 and EMImWF7 are liquids at room temperature whereas EMImPF6 and EMImAsF6 melts at around 330 K. Raman spectra of the obtained salts showed the existence of the EMIm cation and corresponding fluorocomplex anions. IR spectroscopy revealed that strong hydrogen bonds are not observed in these salts. EMImAsF6 (mp 326 K) and EMImSbF6 (mp 283 K) are isostructural with the previously reported EMImPF6. The melting point of the hexafluorocomplex EMIm salt decreases with the increase of the size of the anion (PF6− < AsF6− < SbF6−

Comprehensive and conclusive understanding of the anisotropic upper mantle relies on physical property measurements on high-quality homogeneous specimens of various crystallographic directions. Such specimens are ultimately prepared from one large single crystal. A large olivine single crystal (250 carats) was synthesized for use in property measurements and laboratory experiments including anisotropic studies. We show a new simple and practical method for producing a large single crystal by using the Czochralski-pulling facilities. The quality of the synthetic olivine single crystal was carefully examined by EPMA and X-ray diffractometer, showing a uniform composition and sharp spots of the olivine lattice, respectively. Our new attempts to use natural olivine with a wide iridium crucible are successful, and promising to produce large olivine single crystals successively.

EMIF·HF, 1-ethyl-3-methylimidazolium bifluoride, has been obtained by eliminating HF from a room temperature molten salt EMIF·2.3HF at around 400 K. EMIF·HF crystallizes in space group P21/m with a=7.281(1) A, b=6.762(1) A, c=8.403(1) A, β=107.26(1)°, V=395.09(18) A3, Z=2 at room temperature. The cations are stacked in pillars via the hydrogen bonding between the C4 proton and the ring π-electrons of the adjacent cation. The cations and the anions coupled by strong hydrogen bondings are co-planar.

EUV lithography (EUVL) is well known to be a strong candidate for next generation, single exposure, sub-30nm half-pitch lithography. Much progress relevant to EUVL has been reported for a decade, however, many issues continue to challenge implementation for volume production.[1,2] On the other hand, it seems that the coat develop track process remains very similar and in many aspects returns to KrF or ArF dry process fundamentals, but in practice 26-32nm pitch patterning coat develop track process also has challenges with EUV resist. As access to EUV lithography exposures has become more readily available over the last five (5) years, several challenges and accomplishments in track processing have been reported, such as the improvement of ultra-thin film coating, CD uniformity, defectivity, line width roughness (LWR), and so on.[3,4,5,6] The coat-develop track process has evolved along with novel materials and metrology capability improvements. By coating ultra-thin under layers and resist films and by controlling resist dissolution, the SOKUDO DUO coat develop track system at IMEC (Leuven, Belgium), with ASML NXE3100 exposure, has been used to demonstrate improved CD uniformity, LWR, and defect control. Additionally, we will show the latest lithographic results obtained by novel processing approaches in EUV coat develop track system.

Typical defects to be resolved during coat-develop track processing have been confirmed during each resist generation; I-line, KrF, ArF, ArF immersion, and recently EUVV.[1-5] In this study, two types of defect formation were analyzed: organic film post coating non-uniformity spots and post develop water-marks. During substrate rotation,, a high-speed video camera is used to observe characteristic phenomena which lead to the generation of these rather typical defects. Post coating non-uniformity defects were linked to bubble formation, and post develop defects were associated with thee wafer drying conditions. By correlating high-speed camera images and defect inspection results from several different resists we can disclose the defect generation mechanism of multiple typical phenomena.

Structures of AgAF6 (A=Sb, Ta) have been determined by X-ray single crystal studies at ambient temperatures. AgSbF6 crystallizes in space group Ia 3 with a=979.85(4) pm, V=9.4076(12)×108 pm3, z=8, and AgTaF6 crystallizes in space group P42/mcm with a=499.49(4) pm, c=960.51(8) pm, V=2.3964(6)×108 pm3, z=2. Only the crystal system and cell parameters were obtained for the isomorphic AgNbF6; primitive tetragonal, a=497.80(10) pm, b=960.40(10) pm, V=2.3799(12)×108 pm3, z=2. The results of the Raman spectroscopy of AgAF6 support the obtained structures. The structures are discussed by comparing with that of AgPF6 and AgAsF6 which have recently been determined in a series of our study.

Cyanide-bridged iron-iron and iron--cobalt molecular squares of [Fe(II/4)(mu-CN)4(bpy)8[(PF6)4 x 4H2O (1), [Fe(II/2)Co(II/2)(mu-CN)4(bpy)8](PF6)4 x 3CHCl3 x 2CH3CN (2), and [Fe(II/2)Co(III/2)(mu-CN)4(bpy)8](PF6)6 x 2CHCl3 x 4CH3NO2 (3) (bpy =2,2'-bipyridine) were prepared. X-ray structure analyses for 1-3 were performed and their electrochemistry was studied. In 1-3, four metal ions are bridged by cyanide groups to form tetranuclear macrocycles ("molecular squares"). Each metal ion in the square is six-coordinate: four of the coordination sites are occupied by the nitrogen atoms of two of bpy ligands and the remaining cis coordination sites are occupied by cyanide-carbon or cyanide-nitrogen atoms. In 1, Fe-C (cyanide) (1.899(4)-1.927(4)A) and Fe-N(cyanide) (1.929(4)-1.950(4)A) distances are typical of low-spin Fe2+ ions. In 2, Fe-C(cyanide) and Co(2+)-N(cyanide) bond lengths are in the range 1.919(5)-1.963(5)A and 1.850(5)-2.017(5) A, respectively: in contrast, shorter bond lengths are observed for the metal to cyanide-carbon and cyanide-nitrogen (1.878(7)- 1.893(7) A) in 3. As a result, the molecular squares in 1. 2, and 3 have sides of 4.947(1)4.986(1) A, 5.001(1)-5.053(1) A, and 4.910(1)-4.918(1) A, respectively. Magnetic susceptibility measurements revealed that the Fe2+ and Co3- ions in 1 and 3 are diamagnetic, while the high-spin Co2+ ions in 2 are weakly coupled through the low-spin Fe2 ions. Cyclic voltammograms of the squares are presented, and the electrochemically generated mixed-valent species [Fe(II/2)Fe(III/2)(mu-CN)4(bpy)8]6+ was discussed in terms of the intervalence transfer band.

AgPF6 dissolved in anhydrous HF crystallizes in space group Fm 3 m with a0=755.08(7) pm, V=4.3051(12)×108 pm3 at 25°C, z=4. The structure was determined with the aid of Fourier map and refined to conventional R and Rw values of 0.0812 and 0.0644, respectively. The Ag+ and PF6− ions form a rock salt structure with a threefold orientational disorder of the anion. The distortion of PF6− was scarcely observed. The PF(1) and PF(2) bond lengths are 156 and 159 pm, respectively. AgAsF6 prepared in the same manner is isostructural with AgPF6; a0=775.48(21) pm, V=4.6634(37)×108 pm3 at 25°C, z=4, R=0.0707, Rw=0.0495.

Structures of some alkaline metals and silver(I) hexafluorophosphates, MPF6, have been determined by X-ray single crystallography at ambient temperatures. Although all the salts exhibit a rock salt structure ( Fm 3 m ), three types arise due to the orientational disorders of anions. In NaPF6, Na+ and octahedral PF6− form a linear P–F–Na array without a disorder. PF6− in AgPF6 shows a three-fold orientational disorder described as a rotation by 45° around one of the three crystal axes starting from the original position found in NaPF6. Salts of the heavier alkaline metals are isostructural, showing a four-fold orientational disorder of PF6− described as a rotation by 60° around one of the four diagonals of the crystal lattice from the original orientation in NaPF6.

Reactions of [FeII(CN)2(bpy)2] and [FeIII(CN)2(bpy)2](PF6) with [CuII(bpy)(CH3OH)2](PF6)2 in methanol yielded cyanide-bridged cyclic tetranuclear complexes of [FeII2CuII2(μ-CN)4(bpy)6](PF6)4·2H2O·4CHCl3 (1) and [FeIII2CuII2(μ-CN)4(bpy)6](PF6)6·4CH3CN·2CHCl3 (2), respectively. In the squares of 1 and 2, the Fe2+/3+ (low-spin) and Cu2+ ions are alternately bridged by the cyanide ions, the carbon atoms of which coordinate to the iron ions. Variable-temperature magnetic susceptibility studies of complexes revealed that the Cu2+ ions in 1 are magnetically isolated. In the square of 2, the adjacent Fe3+ and Cu2+ ions were ferromagnetically coupled through the cyanide bridges with a J1 value of +6.3(1) cm-1 and the weaker antiferromagnetic interactions between the orthogonal Fe3+···Fe3+ and Cu2+···Cu2+ pairs are operative (J2 = −3.1(1) cm-1). The propagation of the ferromagnetic interaction in 2 can be understood by the orthogonal magnetic orbitals of the low-spin Fe3+ (dπ) and Cu2+ (dσ) ions. Cyclic voltammogra...

The structure of [NEt4]6[H4Na2(PH)6Mo12O54]·4H2O (1) has been determined by the single-crystal X-ray method. The crystals are monoclinic, space group of C2/c, with cell parameters a = 23.790(3), b = 16.319(2), c = 28.788(3) A, β = 114.365(7)°, and Z = 4. The structure model was refined by full-matrix least squares to R = 0.0624 and Rw = 0.0661 for 6798 independent reflections with Fo > 3σ(F) and in 2θ < 50°. The existence of a meso-type heteropolyion [H4Na2(PH)6Mo12O54]6− (2) in the title crystals has been confirmed. It is composed of a pair of enantiomeric moieties of [H2Na(PH)3Mo6O27]3− (3 and 3i, respectively) which are linked by sharing Na+ ions; here, the superscript i denotes the symmetrical operation code of (1/2−x, 1/2−y, −z). The six MoO6-octahedra contained in the respective moieties are arranged to form Plus- and Minus-helices.

Topological and bond critical point properties of electron density distributions, r(r), were calculated for a series of sulfide molecules, containing first- and second-row main group M-cations. Laplacian maps of the distributions, „ 2 r(r), show that the valence shell charge concentration (VSCC) of the sulfide anion is highly polarized and extended into the internuclear region of the M-S bonds, coalescing with the VSCCs of the more electronegative first-row cations. On the other hand, maps for a corresponding set of oxide molecules show that the oxide anion tends to be less polarized and more locally concentrated in the vicinity of its valence shell, particularly when bonded to second-row M-cations. A search for extrema in the „ 2 r(r) distributions reveals maxima in the VSCCs that can be ascribed to bonded and nonbonded electron pairs. The different and distinctive properties of sulfides and oxides are examined in terms of the number and the positions of the electron pairs and the topographic features of the Laplacian maps. The evidence provided by the electron density distributions and its topological properties indicates that the bonded interactions in sulfides are more directional, for a given M-cation, than in oxides. The value of the electron density distribution at the bond critical point and the length of a given M-S bond are reliable measures of a bonded interaction, the greater the accumulation of the electron density and the shorter the bond, the greater its shared (covalent) interaction.

The bonded radii of anions obtained in topological analyses of theoretical and experimental electron density distributions differ from atomic, ionic and crystal radii in that oxide-, fluoride-, nitride- and sulfide-anion radii are not constant for a given coordination number. They vary in a regular way with bond length and the electronegativity of the cation to which they are bonded, exhibiting radii close to atomic radii when bonded to a highly electronegative cation and radii close to ionic radii when bonded to a highly electropositive cation. The electron density distributions show that anions are not spherical but exhibit several different radii in different bonded directions. The bonded radii of cations correlate with ionic and atomic radii. But unlike ionic radii, the bonded radius of a cation shows a relatively small increase in value with an increase in coordination number. In contrast to atomic and ionic radii, the bonded radius of an ion in a crystal or molecule can be used as a reliable and well-defined estimate of its radius in the direction of its bonds.

Hydrous vanadium (IV, V) oxides containing K or Rb were synthesized by the hydrothermal method from VOSO{sub 4}-M{sub 2}SO{sub 4} (M = K, Rb) solutions. they were found to be isomorphous with previously reported Ba{sub 0.4}V{sub 3}O{sub 8}(VO){sub 0.4}{center_dot}nH{sub 2}O, whose structure consists of V{sub 3}O{sub 8} layers which are bridged by V-O units (denoted by (VO){sub 0.4} in the formula) forming a tunnel-like opening to accommodate hydrous Ba ions. The isomorphous compounds can be formulated by J{sub x}V{sub 3}O{sub 8}(VO){sub y}{center_dot}nH{sub 2}O (M = K, Rb, Ba; n = 0.6--0.7) where x and y show similar values of less than 0.5 as is accounted for by the crystal structure. The formation of this phase seems to be governed by the size of M cation whose ionic radius should lie in a limited range of 1.35 to 1.52 {angstrom}. The V{sub 3}O{sub 8}(VO){sub y} framework structure of a bronze-like type is compared with the V{sub 2}O{sub 5} framework of {beta}-M{sub x}V{sub 2}O{sub 5} ({beta} bronze) and the V{sub 3}O{sub 8} framework of H{sub 2}V{sub 3}O{sub 8}.

EUV lithography (EUVL) is the leading candidate for the manufacture of devices with 1× nm node and beyond. However, many challenges remain for the industry to understand clearly and to overcome before EUVL will be ready for application in volume production. Efforts have been made to improve the various critical components of EUVL, such as light source, exposure tool, mask, resist material, and so on. [1,2] Among these, resist materials are considered as one of the most critical issues in realizing EUVL. [3,4] Coat-develop track system overcame several challenges for each traditional resist system (i.e. i-line, KrF ArF, and ArF immersion). EUV resist system requires ultra thin organic film coating. [5] The under-layer thickness is below 10nm and the resist thickness is about 40nm, however, in some cases film thickness is smaller than the diameter of particles on the substrate, even if the particle size is smaller than the detection limit of defect inspection tool. Also EUV resist patterning becomes extremely small pattern pitch. It leads the difficulty of CD control because the resist solubility in develop processing depends on resist type. Some resists were significantly swelled during develop process. Swelling depends on develop time and developer materials. That behavior on EUV resist system is becoming evident. [6] Furthermore, LWR improvement on track processing is required. During the conference, we will discuss how to coat the substrate with ultra thin film and how to control resist dissolution to improve CD uniformity and LWR. Additionally, we will show the latest lithographic results obtained with the novel application for EUV coat-develop track system.

A new layered vanadium bronze designated as σ-phase Zn0.25V2O5· H2O has been hydrothermally synthesized from ZnCl2and VO(OH)2. A single-crystal study revealed the triclinic systemP 1 :a= 10.614(2) A,b= 8.031(3) A,c= 10.7688(9) A, α = 90.65(1)°, β = 91.14(1)°, γ = 90.09(2)°, andZ= 8. The structure was solved and refined toR/Rw= 0.079/0.048 for 1580 reflections withI> 3σ(I), which consists of V2O5layers stacking along thecaxis and interstitial hydrated Zn2+ions. The V2O5layer adopts a novel polyhedral framework built up of VO6octahedra, VO5trigonal bipyramids, and VO4tetrahedra. When projected parallel to theabplane, the V2O5layer is described by the atomic sheet model in a manner similar to the V2O5layer of δ phase such as δ-AgxV2O5, that is, a double-sheet type composed of two V2O5sheets facing each other. The interstitial Zn atom forms a ZnO6octahedron with two apical oxygens of the VO4tetrahedra on opposide sides and with four coplanar water molecules. The anhydrous σ phase was obtained by heating the hydrate up to 200°C accompanied by the contraction in layer spacing from 10.76 to 8.92 A.

The crystal structure of K–Cr oxide of hollandite type synthesized under high pressure and high temperature was determined by the single crystal X-ray diffraction method. The compound crystallizes with the tetragonal symmetry of the space group I 4/ m , the cell parameters a = 9.7627(4) and c = 2.9347(6) A, and Z = 1. The structure refinement based on 572 unique reflections (2θ R = 0.0296. The experiment confirmed that the chemical composition was stoichiometric, K 2 Cr 8 O 16 , in which the tunnel sites were fully occupied by K ions without displacement from the special position (2 b ). The result suggests that the high pressure induces a high cation occupancy in the tunnel and opens a way to control the occupancy and some physical properties related to tunnel cations.

The structure of [NBun4]2[SMo12O40] has been determined by the single-crystal X-ray method: cubic, space group Fm3m, a= 18.824(1)A and Z= 4. The structure model was refined by full-matrix least squares to R= 0.0607 and R′= 0.0585 for 320 independent reflections and 32 variables. The heteropolyion [SMo12O40]2–1 contained in the crystals is a typical Keggin molecule with point symmetry 3m and located at sites of crystallographic Fm3m symmetry in two equally weighted orientations related by inversion at the S atom. The geometry is compared with those of the isomorphous Keggin molecules [PMo12O40]3–2, [SiMO12O40]4–3 and [GeMo12O40]4–4 as a function of the nature of the central heteroatom and in relation to the relative stability 123 < 4 in aqueous solution.

A new barium vanadium oxide Ba 0.4 V 3 O 8 (VO) 0.4 · n H 2 O ( n ∼ 0.6) has been synthesized hydrothermally from a VOCl 2 -BaCl 2 solution. The green-black crystal composed of elongated thin plates exhibits a monoclinic system: P 2 1 / m , a = 10.153(3) A, b = 3.6329(9) A, c = 9.435(2) A, and β = 102.10(2)°. Structural analysis using 951 independent reflections led to R = 0.063 and R w = 0.076. The structure is basically a layered type made up of V 3 O 8 layers with interstitial Ba 2+ ions and water molecules. Its striking feature is that the V 3 O 8 layers are bridged imperfectly by partially absent VO 5 trigonal bipyramids which form tunnel-like openings. The structure is thus regarded as an intermediate between layered and tunnel structure types. Interstitial Ba 2+ ions were observed to be displaced from the position on the mirror plane.

Racemic samples of novel chiral cyclic nitroxides 2-(4-hydroxyphenyl)-2,5,5-trimethylpyrrolidine-1-oxy 1, trans-2-(4-hydroxyphenyl)-2,5-dimethyl-5-phenylpyrrolidine-1-oxy 2 and trans-2,5-bis(4-hydroxyphenyl)-2,5-dimethylpyrrolidine-1-oxy 3 having 4-hydroxyphenyl groups on the stereogenic centres adjacent to the NO radical moiety have been found to exist as racemic conglomerates in the crystalline state, and the origin of the conglomerate formation has been studied by X-ray crystallographic analysis and magnetic susceptibility measurements.

Single crystals of a new barium-manganese oxide were grown under hydrothermal conditions at 600°C and 0.2 GPa. The chemical composition determined by X-ray analysis is BaMn3O5(OH). The compound crystallizes in the orthorhombic system (space group Immm) with a basic cell of a = 19.355(3) A, b = 4.531(1) A, c = 2.791(1) A, and Z = 2. The structure exposes a supercell with twice the volume of the basic cell and monoclinic symmetry (a = 19.554(3) A, b = 4.531(1) A, c = 5.581(1) A, β = 98.20(1)°, Z = 4, space group C2/m). The crystal structure was determined by the Patterson method and refined to R = 0.038 based on 1184 independent reflections. The structure consists of ribbons composed of four parallel chains of edge-sharing MrO6 octahedra running along [001] and parallel to the (010) plane. The two outer chains of the ribbon are complete. One out of two Mn ions is missing in the two inner chains. In these octahedra the corner-sharing oxygens are replaced by Ba. The MnO6 octahedra are highly distorted and indicate the trivalent state of Mn. Valence balance at the site and large temperature factors are clear evidence of a replacement of one of seven independent oxygens by OH.

The structure of [NEt4]6[H4Na2(PH)6Mo12O54]·4H2O (1) has been determined by the single-crystal X-ray method. The crystals are monoclinic, space group of C2/c, with cell parameters a = 23.790(3), b = 16.319(2), c = 28.788(3) A, β = 114.365(7)°, and Z = 4. The structure model was refined by full-matrix least squares to R = 0.0624 and Rw = 0.0661 for 6798 independent reflections with Fo > 3σ(F) and in 2θ < 50°. The existence of a meso-type heteropolyion [H4Na2(PH)6Mo12O54]6− (2) in the title crystals has been confirmed. It is composed of a pair of enantiomeric moieties of [H2Na(PH)3Mo6O27]3− (3 and 3i, respectively) which are linked by sharing Na+ ions; here, the superscript i denotes the symmetrical operation code of (1/2−x, 1/2−y, −z). The six MoO6-octahedra contained in the respective moieties are arranged to form Plus- and Minus-helices.

Structures of some alkaline metals and silver(I) hexafluorophosphates, MPF6, have been determined by X-ray single crystallography at ambient temperatures. Although all the salts exhibit a rock salt structure ( Fm 3 m ), three types arise due to the orientational disorders of anions. In NaPF6, Na+ and octahedral PF6− form a linear P–F–Na array without a disorder. PF6− in AgPF6 shows a three-fold orientational disorder described as a rotation by 45° around one of the three crystal axes starting from the original position found in NaPF6. Salts of the heavier alkaline metals are isostructural, showing a four-fold orientational disorder of PF6− described as a rotation by 60° around one of the four diagonals of the crystal lattice from the original orientation in NaPF6.

AgPF6 dissolved in anhydrous HF crystallizes in space group Fm 3 m with a0=755.08(7) pm, V=4.3051(12)×108 pm3 at 25°C, z=4. The structure was determined with the aid of Fourier map and refined to conventional R and Rw values of 0.0812 and 0.0644, respectively. The Ag+ and PF6− ions form a rock salt structure with a threefold orientational disorder of the anion. The distortion of PF6− was scarcely observed. The PF(1) and PF(2) bond lengths are 156 and 159 pm, respectively. AgAsF6 prepared in the same manner is isostructural with AgPF6; a0=775.48(21) pm, V=4.6634(37)×108 pm3 at 25°C, z=4, R=0.0707, Rw=0.0495.

The structure of Na[NMe4]3S2Mo5O23·4H2O has been determined by the single-crystal X-ray method: monoclinic, space group P2/c, a= 29.25(2), b= 12.85(1), c= 18.24(1)A, and β= 123.89(2)° and Z= 6. The structure was refined by full-matrix least squares to R′= 0.0678 for 5532 reflections. The existence of the Strandberg-type heteropolyion [S2Mo5O23]4–1 in the crystals has been confirmed. The geometry of 1 was compared systematically with various analogues containing SIVO32–, PO43–, MePO32– or NH3C2H4PO3– as the central polyhedron. The UV spectrum of the salts Na[NMe4]3S2Mo5O23·4H2O and [NMe4]4S2Mo5O23 in neat MeCN, hence the kernel heteropolyion 1 showed absorption maxima at λ= 213 and 243 nm (Iµ= 3.2 × 104 and 3.3 × 104 dm3 mol–1 cm–1). Spectroscopic measurements also indicate that 1 and [Mo6O19]2– form simultaneously in aqueous–MeCN media containing MoVI and H2SO4.

Electrostatic energies of nine mantle minerals in the MgO–SiO2 system (forsterite, modified spinel, spinel, orthoenstatite, clinoenstatite, ilmenite, perovskite, periclase and stishovite) were calculated by the method of Bertaut (1952) with error estimations.It is noted that the structure of ortho- and clinoenstatites have atomic geometries which are skillfully arranged to gain low electrostatic energies compared with ilmenite and perovskite, although the former minerals have lower densities than the latter. This low energy results from the low values of Mg1, O3A and O3B ions in these pyroxenes but mainly from the fact that O2A and O2B oxygens, which are “undersaturated” with Pauling’s bond-strength sums, do not have so high values as O1 of modified spinel which are also “undersaturated” with them.Periclase and hence, Mg and O of the mineral exhibit an extremely high same value, showing a clear contrast with other minerals even in the high pressure. This indicates that Fe2+ ion prefers magnesiowustite (which is isostructural with periclase) in the cation distributions of Fe2+ and Mg2+ between perovskite and magnesiowustite, and spinel and magnesiowustite which might coexist in the mantle transition zone. This is qualitatively consistent with the high pressure experiments studied by high pressure workers.

The introduction of Immersion lithography, combined with the desire to maximize the number of potential yielding devices per wafer, has brought wafer edge engineering to the forefront for advanced semiconductor manufactures. Bevel cleanliness, the position accuracy of the lithography films, and quality of the EBR cut has become more critical. In this paper, the effectiveness of wafer track based solutions to enable state-of-art bevel schemes is explored. This includes an integrated bevel cleaner and new bevel rinse nozzles. The bevel rinse nozzles are used in the coating process to ensure a precise, clean film edge on or near the bevel. The bevel cleaner is used immediately before the wafer is loaded into the scanner after the coating process. The bevel cleaner shows promise in driving down defectivity levels, specifically printing particles, while not damaging films on the bevel.

In immersion lithography process, film stacking architecture will be necessary due to film peeling. However, the architecture will restrict lithographic area within a wafer due to top side EBR accuracy In this paper, we report an effective film stacking architecture that also allows maximum lithographic area. This study used a new bevel rinse system on RF3 for all materials to make suitable film stacking on the top side bevel. This evaluation showed that the new bevel rinse system allows the maximum lithographic area and a clean wafer edge. Patterning defects were improved with suitable film stacking.

Single crystals of Rb1.5Mn8O16 were grown under the hydrothermal conditions of 450°C and 0.2GPa. The structure was tetragonal (I4/m); a=9.915(9)A, c=2.866(3)A and Z=1. The X-ray structure analysis was performed using the 656 independent reflections to R=0.088 and Rw=0.054. The determined structure adopts hollandite type characterized by the 2×2 tunnel. It is noted the electron density distribution of Rb+ in the tunnel was elongated along the c-axis, suggesting the distribution of Rb+ over the special position (2b).

Recently, pattern collapse is becoming one of the critical issues in semiconductor manufacturing and many works have been done to solve this issue 1 ) 2 ). Since pattern collapse occurs when outer force onto the resist pattern such as surface tension, impact of rinse solution, etc. surpasses the resistance of the resist pattern such as mechanical strength, adhesion force between resist and substrate, it is considered effective for improvement of pattern collapse to control resist film properties by track process, i.e., optimization of the mechanical properties of the resist film and enhancement of the adhesion force between resist and substrate 3 ) -5 ). In this study, we focused on the mechanical strength of the resist film and examined how post applied bake (PAB) condition affects the pattern collapse behavior. From ellipsometry measurement, it was found that increasing PAB time and temperature resulted in thickness reduction and refractive index increase, which suggested that the density of the resist film became high. Then we analyzed the mechanical strength of the resist film with the tip indentation method using atomic force microscope. It was found that the hardness of the resist film was affected by PAB conditions and regardless of PAB condition, hardened layer existed beneath the film surface. Finally, we carried out the measurements of loads to collapse 180nm resist dot patterns using the direct peeling with atomic force microscope tip (DPAT) method. Loads ranged from 600 to 2000nN overall and essentially increased as seen for indentation measurements when PAB temperature or time was increased, except some critical conditions. Through these evaluations using AFM, we succeeded in quantitatively evaluate the mechanical properties of the resist films processed with various PAB conditions. It was found that PAB condition obviously impacts on the hardness of the resist film and it is closely related to pattern collapse load.

In immersion lithography technique, some defects such as a watermark and a nanoscale bubble have been focused as the serious problems to be solved. In order to clarify the formation mechanism of the watermark, the in-situ observation of the drying behavior of the water drop containing the particles and without the particles, are conducted on the Si substrates. In the static watermark formation on the flat substrate, we can classify the watermark formation processes based on the watermark shapes. From the surface energy balance analysis, the particles dispersed in the DI-water adhere on the Si substrate. In addition, from the Laplace force balance, the particles adhered on the Si substrate will attract the surrounding particles. Hence, we can clarify the formation mechanism of the static watermark condensed in the ring shape. Meanwhile, in the dynamic watermark formation, we can observe clearly the condensed watermark is formed on the Si substrate and the particles move to lower region in inclined drop. In actual immersion lithography system, we can discuss the particles are more likely to remain in the immersion liquid under the lens system.

It is necessary to develop a nano-bubble detector similar as a conventional particle counter for reducing micro and nano defects caused by nano-bubble (NB) in immersion lithography. In this regard, we discuss adhesion and removal mechanisms of NB adhered on a resist surface for immersion lithography. The micro and nano bubbles are more likely to adhere to the micro defect on the resist surface and lens surface. Keeping cleanness of lens and resist surface is necessary in order to prevent the micro bubble adhesion. We employed the AFM (Atomic Force Microscope) for the observation of NBs on a Si substrate and a resist surface. The diameter and height of NBs observed are approximately 40~100nm and 3~8nm, respectively. By approaching the AFM tip onto the NBs, the repulsive force can be detected but the attractive force on the resist surface. The interaction analysis between the AFM tip and the ArF excimer resist surface is effective in order to identify the NBs and to distinguish from solid particles. These phenomena can be discussed on the basis of Lifshitz theory. The separation procedure of the NB is accomplished with the AFM tip. The applying load at which the NB can be separated into the minute one is approximately 5nN. In addition, by the thermodynamic analysis, it can be considered that the NB adhered on the resist surface tends to be a flat shape and spread on the resist surface. It is difficult to adhere the bubbles on the resist surface.

The micro bubbles condense in the concave channel and are trapped at the channel corner. In the experiments, the deionized (DI) water is dropped on a dry film resist (DFR) pattern. In the result, the micro bubble condensed and trapped at the different position in various shape patterns. The removal of micro bubbles adhered on a resist pattern has been recognized as one important factor in micro device manufacturing. We explained the condensation behavior of the micro bubble based on thermodynamics. The force acting on the bubble is estimated based on the force balance model between buoyancy and line tension. We can control and predict the micro bubble condensation by designing micro pattern arrangement.

Mechanical strength of resist film processed by various post apply bake (PAB) conditions were measured utilizing the tip indentation method using atomic force microscope (AFM). With the tip indentation method, we could quantify mechanical strength of resist film in terms of “degree of softening.” It was found that PAB at our standard baking temperature tends to lead to softening of the resist film which is considered due to existence of softening point of the resist polymer. Also changing baking time at this temperature showed very complicated softness behavior. By control of baking temperature, we could obtain harder resist film as baking time becomes longer. Further analysis of these resist film properties by ellipsometry suggested that changes in mechanical strength occur by the evaporation of the resist solvent and/or structure changes inside the resist film, depending upon baking conditions.

Adhesion property of resist is characterized with DPAT (direct peeling with atomic force microscope (AFM) tip) method using 193 nm resist patterns of 180 nm dot shape which were developed for various developing time between 12 and 120 seconds in order to analyze the phenomenon which the short develop time process had led to suppress the pattern collapse. Surface free energy and refractive index of resist film treated with the developing time were also investigated from a thermodynamic point of view. The balance model among surface energy was adopted for analyzing intrusion phenomenon of developer solution into the resist-substrate interface. It can be explained quantitatively that the intrusion energy of developer solution acts to weaken the adhesion strength of resist pattern to the substrate. Furthermore, the intrusion energy became larger with increasing developing time. Analysis with the DPAT method indicates that the pattern collapse occurs accompanied with interface and cohesion destruction. Interface-scientifically speaking, the short develop time process proved to be effective to suppress the pattern collapse because of higher adhesion energy of the resist pattern to the substrate in shorter developing time.

Various sizes of concave square patterns are used for microscale bubble adhesion and removal investigation in a water/methanol mixture solution. As decreasing the surface energy of the solution, the micro bubbles are more likely to remove from the square patterns. However, the micro bubble is less likely to remove as decreasing the square size of patterns. The threshold concentration of water/methanol solution for bubble removal can be determined experimentally. Based on the surface energy analysis, the adhesion and removal mechanisms of micro bubble can be explained. The nanoscale bubbles adhered on an ArF excimer resist surface can be observed clearly by using atomic force microscope (AFM). The growth of bubbles on the ArF excimer resist surface can be imaged. By the AFM technique, nanoscale bubble can be divided into some minute bubbles on the ArF resist surface under applying certain force about 5nN. The condensation nature of nanoscale bubbles is discussed.