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Title: Synthesis and structural characterization of Al{sub 7}C{sub 3}N{sub 3}-homeotypic aluminum silicon oxycarbonitride, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5)

Abstract

A new aluminum silicon oxycarbonitride, (Al{sub 5.8}Si{sub 1.2})(O{sub 1.0}C{sub 3.5}N{sub 1.5}), has been synthesized and characterized by X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). The title compound is hexagonal with space group P6{sub 3}/mmc and unit-cell dimensions a=0.322508(4) nm, c=3.17193(4) nm and V=0.285717(6) nm{sup 3}. The atom ratios of Al:Si and those of O:C:N were, respectively, determined by EDX and EELS. The initial structural model was successfully derived from the XRPD data by the direct methods and further refined by the Rietveld method. The crystal is most probably composed of four types of domains with nearly the same fraction, each of which is isotypic to Al{sub 7}C{sub 3}N{sub 3} with space group P6{sub 3}mc. The existence of another new oxycarbonitride (Al{sub 6.6}Si{sub 1.4})(O{sub 0.7}C{sub 4.3}N{sub 2.0}), which must be homeotypic to Al{sub 8}C{sub 3}N{sub 4}, has been also demonstrated by XRPD and TEM. - Graphical abstract: A new oxycarbonitride discovered in the Al-Si-O-C-N system, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5). The crystal is composed of four types of domains (I, II, III and IV), and hence the structure is represented by a split-atom model.more » Individual crystal structures can be regarded as layered structures, which consist of A-type [(Al, Si){sub 4}(O, C, N){sub 4}] unit layers and B-type [(Al, Si)(O, C, N){sub 2}] single layers. Highlights: > (Al{sub 5.8}Si{sub 1.2})(O{sub 1.0}C{sub 3.5}N{sub 1.5}) as a new aluminum silicon oxycarbonitride. > Crystal structure is determined and represented by a split-atom model. > Existence of another new oxycarbonitride (Al{sub 6.6}Si{sub 1.4})(O{sub 0.7}C{sub 4.3}N{sub 2.0}) is demonstrated. > Both new materials are formed by oxidation and nitridation of (Al, Si){sub 6}(O, C){sub 5}.« less

Authors:
; ;  [1];  [2];  [1]
  1. Department of Environmental and Materials Engineering, Nagoya Institute of Technology, Nagoya 466-8555 (Japan)
  2. Cooperative Research Facility Center, Toyohashi University of Technology, Toyohashi 441-8580 (Japan)
Publication Date:
OSTI Identifier:
21580203
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 184; Journal Issue: 8; Other Information: DOI: 10.1016/j.jssc.2011.06.030; PII: S0022-4596(11)00358-6; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALUMINIUM; CRYSTALS; DOMAIN STRUCTURE; ENERGY-LOSS SPECTROSCOPY; HCP LATTICES; LATTICE PARAMETERS; LAYERS; NITRIDATION; OXIDATION; SILICON; SPACE GROUPS; STRUCTURAL MODELS; SYNTHESIS; TRANSMISSION ELECTRON MICROSCOPY; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY; CHEMICAL REACTIONS; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DIFFRACTION; ELECTRON MICROSCOPY; ELECTRON SPECTROSCOPY; ELEMENTS; HEXAGONAL LATTICES; METALS; MICROSCOPY; SCATTERING; SEMIMETALS; SPECTROSCOPY; SYMMETRY GROUPS

Citation Formats

Urushihara, Daisuke, Kaga, Motoaki, Asaka, Toru, Nakano, Hiromi, and Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp. Synthesis and structural characterization of Al{sub 7}C{sub 3}N{sub 3}-homeotypic aluminum silicon oxycarbonitride, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5). United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.06.030.
Urushihara, Daisuke, Kaga, Motoaki, Asaka, Toru, Nakano, Hiromi, & Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp. Synthesis and structural characterization of Al{sub 7}C{sub 3}N{sub 3}-homeotypic aluminum silicon oxycarbonitride, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5). United States. doi:10.1016/j.jssc.2011.06.030.
Urushihara, Daisuke, Kaga, Motoaki, Asaka, Toru, Nakano, Hiromi, and Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp. Mon . "Synthesis and structural characterization of Al{sub 7}C{sub 3}N{sub 3}-homeotypic aluminum silicon oxycarbonitride, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5)". United States. doi:10.1016/j.jssc.2011.06.030.
@article{osti_21580203,
title = {Synthesis and structural characterization of Al{sub 7}C{sub 3}N{sub 3}-homeotypic aluminum silicon oxycarbonitride, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5)},
author = {Urushihara, Daisuke and Kaga, Motoaki and Asaka, Toru and Nakano, Hiromi and Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp},
abstractNote = {A new aluminum silicon oxycarbonitride, (Al{sub 5.8}Si{sub 1.2})(O{sub 1.0}C{sub 3.5}N{sub 1.5}), has been synthesized and characterized by X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). The title compound is hexagonal with space group P6{sub 3}/mmc and unit-cell dimensions a=0.322508(4) nm, c=3.17193(4) nm and V=0.285717(6) nm{sup 3}. The atom ratios of Al:Si and those of O:C:N were, respectively, determined by EDX and EELS. The initial structural model was successfully derived from the XRPD data by the direct methods and further refined by the Rietveld method. The crystal is most probably composed of four types of domains with nearly the same fraction, each of which is isotypic to Al{sub 7}C{sub 3}N{sub 3} with space group P6{sub 3}mc. The existence of another new oxycarbonitride (Al{sub 6.6}Si{sub 1.4})(O{sub 0.7}C{sub 4.3}N{sub 2.0}), which must be homeotypic to Al{sub 8}C{sub 3}N{sub 4}, has been also demonstrated by XRPD and TEM. - Graphical abstract: A new oxycarbonitride discovered in the Al-Si-O-C-N system, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5). The crystal is composed of four types of domains (I, II, III and IV), and hence the structure is represented by a split-atom model. Individual crystal structures can be regarded as layered structures, which consist of A-type [(Al, Si){sub 4}(O, C, N){sub 4}] unit layers and B-type [(Al, Si)(O, C, N){sub 2}] single layers. Highlights: > (Al{sub 5.8}Si{sub 1.2})(O{sub 1.0}C{sub 3.5}N{sub 1.5}) as a new aluminum silicon oxycarbonitride. > Crystal structure is determined and represented by a split-atom model. > Existence of another new oxycarbonitride (Al{sub 6.6}Si{sub 1.4})(O{sub 0.7}C{sub 4.3}N{sub 2.0}) is demonstrated. > Both new materials are formed by oxidation and nitridation of (Al, Si){sub 6}(O, C){sub 5}.},
doi = {10.1016/j.jssc.2011.06.030},
journal = {Journal of Solid State Chemistry},
number = 8,
volume = 184,
place = {United States},
year = {Mon Aug 15 00:00:00 EDT 2011},
month = {Mon Aug 15 00:00:00 EDT 2011}
}
  • We have prepared a new layered oxycarbide, [Al{sub 5.25(5)}Si{sub 0.75(5)}][O{sub 1.60(7)}C{sub 3.40(7)}], by isothermal heating of (Al{sub 4.4}Si{sub 0.6})(O{sub 1.0}C{sub 3.0}) at 2273 K near the carbon-carbon monoxide buffer. The crystal structure was characterized using X-ray powder diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy (EDX). The title compound is trigonal with space group R3m (centrosymmetric), Z=3, and hexagonal cell dimensions a=0.32464(2) nm, c=4.00527(14) nm and V=0.36556(3) nm{sup 3}. The atom ratios Al:Si were determined by EDX, and the initial structural model was derived by the direct methods. The final structural model showed the positional disordering of one ofmore » the three types of Al/Si sites. The reliability indices were R{sub wp}=4.45% (S=1.30), R{sub p}=3.48%, R{sub B}=2.27% and R{sub F}=1.25%. The crystal is composed of three types of domains with nearly the same fraction, one of which has the crystal structure of space group R3-bar m. The crystal structure of the remaining two domains, which are related by pseudo-symmetry inversion, is noncentrosymmetric with space group R3m. - Graphical Abstract: A new aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6). The crystal is composed of three types of domains (I, II and III), and hence the structure is represented by a split-atom model. Individual crystal structures can be regarded as layered structures, which consist of A-type [(Al,Si){sub 4}(O,C){sub 4}] unit layers and B-type [(Al,Si)(O,C){sub 2}] single layers.« less
  • A new quaternary layered oxycarbide, [Al{sub 4.39(5)}Si{sub 0.61(5)}]{sub S}IGMA{sub 5}[O{sub 1.00(2)}C{sub 2.00(2)}]{sub S}IGMA{sub 3}C, has been synthesized and characterized by X-ray powder diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy (EDX). The title compound was found to be hexagonal with space group P6{sub 3}/mmc, Z=2, and unit-cell dimensions a=0.32783(1) nm, c=2.16674(7) nm and V=0.20167(1) nm{sup 3}. The atom ratios Al:Si were determined by EDX, and the initial structural model was derived by the direct methods. The final structural model showed the positional disordering of one of the three types of Al/Si sites. The maximum-entropy methods-based pattern fitting (MPF) methodmore » was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The reliability indices calculated from the MPF were R{sub wp}=3.73% (S=1.20), R{sub p}=2.94%, R{sub B}=1.04% and R{sub F}=0.81%. The crystal was an inversion twin. Each twin-related individual was isostructural with Al{sub 4}SiC{sub 4} (space group P6{sub 3}mc, Z=2). - Graphical abstract: A new oxycarbide discovered in the Al-Si-O-C system, Al{sub 4}SiC{sub 4}-homeotypic [Al{sub 4.4}Si{sub 0.6}][O{sub 1.0}C{sub 2.0}]C. The crystal is an inversion twin, and hence the structure is represented by a split-atom model. The three-dimensional electron density distributions are determined by the maximum-entropy methods-based pattern fitting, being consistent with the disordered structural model.« less
  • A new aluminum oxycarbonitride, Al{sub 5}(O{sub x}C{sub y}N{sub 4-x-y}) (x{approx}1.4 and y{approx}2.1), has been synthesized and characterized by X-ray powder diffraction, transmission electron microscopy and electron energy loss spectroscopy (EELS). The title compound was found to be hexagonal with space group P6{sub 3}/mmc, Z=2, and unit-cell dimensions a=0.328455(6) nm, c=2.15998(3) nm and V=0.201805(6) nm{sup 3}. The atom ratios O:C:N were determined by EELS. The final structural model, which is isomorphous with that of (Al{sub 4.4}Si{sub 0.6})(O{sub 1.0}C{sub 3.0}), showed the positional disordering of one of the three types of Al sites. The maximum-entropy method-based pattern fitting (MPF) method was usedmore » to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The reliability indices calculated from the MPF were R{sub wp}=6.94% (S=1.22), R{sub p}=5.34%, R{sub B}=1.35% and R{sub F}=0.76%. The crystal was an inversion twin. Each twin-related individual was isostructural with Al{sub 5}C{sub 3}N (space group P6{sub 3}mc, Z=2). - Graphical abstract: A new oxycarbonitride discovered in the Al-O-C-N system, Al{sub 5}(O{sub 1.4}C{sub 2.1}N{sub 0.5}). The crystal is an inversion twin, and hence the structure is represented by a split-atom model. The three-dimensional electron density distributions are determined by the maximum-entropy methods-based pattern fitting, being consistent with the disordered structural model. Display Omitted« less
  • The crystal structure, electronic structure, and photoluminescence properties of Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} (x=0-0.1, 0<z<1) and Eu{sub x}M{sub y}Si{sub 6-z}Al{sub z-x-y}O{sub z+x+y}N{sub 8-z-x-y} (M=2Li, Mg, Ca, Sr, Ba) have been studied. Single-phase Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} can be obtained in very narrow ranges of x{<=}0.06 (z=0.15) and z<0.5 (x=0.3), indicating that limited Eu{sup 2+} ions can be incorporated into nitrogen-rich Si{sub 6-z}Al{sub z}O{sub z}N{sub 8-z}. The Eu{sup 2+} ion is found to occupy the 2b site in a hexagonal unit cell (P6{sub 3}/m) and directly connected by six adjacent nitrogen/oxygen atoms ranging 2.4850-2.5089 A. The calculatedmore » host band gaps by the relativistic DV-X{alpha} method are about 5.55 and 5.45 eV (without Eu{sup 2+} 4f5d levels) for x=0 and 0.013 in Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} (z=0.15), in which the top of the 5d orbitals overlap with the Si-3s3p and N-2p orbitals within the bottom of the conduction band of the host. Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} shows a strong green emission with a broad Eu{sup 2+} band centered at about 530 nm under UV to near-UV excitation range. The excitation and emission spectra are hardly modified by Eu concentration and dual-doping ions of Li and other alkaline-earth ions with Eu. Higher Eu concentrations can significantly quench the luminescence of Eu{sup 2+} and decrease the thermal quenching temperature. In addition, the emission spectrum can only be slightly tuned to the longer wavelengths ({approx}529-545 nm) by increasing z within the solid solution range of z<0.5. Furthermore, the luminescence intensity of Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} can be improved by increasing z and the dual-doping of Li and Ba. - Graphical abstract: Excitation and emission spectra of Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} with the project of a 2x2x2 supercell crystal structure viewed along (001), in which red spheres are the Eu atoms.« less
  • The reactions of the cis-dioxorhenium(VII)-catecholate complex [(CH{sub 3}CH{sub 2}){sub 4}N][ReO{sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (1) with either monosubstituted organohydrazines (C{sub 6}H{sub 5}NHNH{sub 2}; 4-BrC{sub 6}H{sub 4}NHNH{sub 2}) or 1,1 disubstituted organohydrazines (Ph{sub 2-}NNH{sub 2}) yield the cis-bis(diazenido) core complexes [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNR){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (5, R = C{sub 6}H{sub 5}; 6, R = 4-BrC{sub 6}H{sub 4}) and the cis-bis(hydrazido) core species [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNPh{sub 2}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}] (7). Elution of 5 in a 3:1 mixture of toluene/methanol on a column of silica gel resulted in cation exchange to givemore » Na[Re(NNPh){sub 2}-(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{center_dot}CH{sub 3}CN (8) as a one-dimensional polymer ([Na(CH{sub 3}CN)]{sup +}[Re(NNPh){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{sup {minus}}){sub 2}. Crystal data for C{sub 32}H{sub 38}N{sub 5}O{sub 4}Re (5): P2{sub 1}/c,a = 14.458(3) {angstrom}, b = 10.436(2) {angstrom}, c = 21.767(4) {angstrom}, {beta} = 107.04(3){degrees}, V = 3140(2) {angstrom}{sup 3}, Z = 4, D {sub calc} = 1.572 g cm{sup {minus}3}; structure solution and refinement based on 3256 reflections with I{sub o} {ge} 3{sigma}(I{sub o}) converged at R = 0.053. Crystal data for C{sub 44}H{sub 48}N{sub 5}O{sub 4}Re (7): P1, a = 11.660(2) {angstrom}, b = 11.864(2) {angstrom}, c = 15.400(2) {angstrom}, {alpha} = 107.12(3){degrees}, {beta} = 94.99(3){degrees}, {gamma} = 97.61(3){degrees}, V = 2000(1) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.490 g cm{sup {minus}3}; 3702 reflections, R = 0.0534. Crystal data for C{sub 26}H{sub 18}N{sub 5}NaO{sub 4}Re (8): P2/n, a = 5.785(1) {angstrom}, b = 9.670(2) {angstrom}, c = 23.142(5) {angstrom}. {beta} = 90.91(30)degrees, V = 1294.4(7) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.737 g cm{sup {minus}3}; 1517 reflections, R = 0.049.« less