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SnGe4N4O4 was synthesized at high pressure (16 and 20 GPa) and high temperature (1200 and 1500°C) in a large‐volume press. Powder X‐ray diffraction experiments using synchrotron radiation indicate that the derived samples are mixtures of known and unknown phases. However, the powder X‐ray diffraction patterns are not sufficient for structural characterization. Transmission electron microscopy studies reveal crystals of several hundreds of nanometres in size with different chemical composition. Among them, crystals of a previously unknown phase with stoichiometry SnGe4N4O4 were detected and investigated using automated diffraction tomography (ADT), a three‐dimensional electron diffraction method. Via ADT, the crystal structure could be determined from single nanocrystals in space group P63mc, exhibiting a nolanite‐type structure. This was confirmed by density functional theory calculations and atomic resolution scanning transmission electron microscopy images. In one of the syntheses runs a rhombohedral 6R polytype of SnGe4N4O4 could be found together with the nolanite‐type SnGe4N4O4. The structure of this polymorph was solved as well using ADT. [ABSTRACT FROM AUTHOR]

Naturally occurring single crystals of bixbyite, (Fe,Mn)2O3, from the Thomas Mountain Range in Utah, U.S.A., were studied via (scanning) transmission electron microscopy (S)TEM. With up to 5 cm edge length, these mineral specimens are the largest bixbyite crystals found worldwide. Their hexahedral shapes are often modified by {211} facets at the corners and small {211} truncations along their cube edges. Characteristic lamellar defects, running parallel to the {100} planes, can be observed via TEM imaging. The defects are, according to EDS analyses, attributed to the tetragonal manganese silicate braunite, Mn7[SiO12]. In the present study, electron nano-diffraction and atomic resolution (S)TEM were employed to verify the presence of braunite lamellae and to investigate their orientation relationship with bixbyite. The analysis confirmed an epitaxial intergrowth of both phases, with their main-axes being parallel and the unique c-axis of braunite always aligned perpendicularly to the lamellar plane. Moreover, small rectangular-shaped precipitates, which had been, due to their almost identical chemical composition, previously interpreted as small bixbyite inclusions within the host crystal, were often observed in contact with the braunite lamellae. Electron nano-diffraction and atomic resolution (S)TEM imaging revealed these crystallites not to be bixbyite but jacobsite, a cubic iron-manganese spinel with the stoichiometric formula MnFe2O4, whose occurrence in this unique context had not been reported before. Moreover, due to the higher temperatures needed for spinel crystallization, the occurrence of jacobsite may serve as a geo-thermometer. (S)TEM in conjunction with automated crystal orientation mapping (ACOM)-TEM showed that no orientation relationship exists between the jacobsite inclusions and the bixbyite/braunite matrix. Nevertheless, their characteristic rectangular shape is typically aligned concordantly with the (001) plane of the braunite lamellae. The resulting crystal shape of jacobsite is determined by the presence of the braunite lamellae, while the respective crystallites maintain their freedom of rotation. To the authors' knowledge, this is a novel observation of exomorphosis of jacobsite, i.e., the change in the habit of the spinel crystallites due to external conditions. Note that the term "exomorphosis" is used here in the mineralogical sense in contrast to the often-used petrological aspect. Based on the TEM results, the formation of the jacobsite precipitates is discussed and a growth model suggested. [ABSTRACT FROM AUTHOR]

We report the first oxynitride of tin, Sn2N2O (SNO), exhibiting a Rh2S3‐type crystal structure with space group Pbcn. All Sn atoms are in six‐fold coordination, in contrast to Si in silicon oxynitride (Si2N2O) and Ge in the isostructural germanium oxynitride (Ge2N2O), which appear in four‐fold coordination. SNO was synthesized at 20 GPa and 1200–1500 °C in a large volume press. The recovered samples were characterized by synchrotron powder X‐ray diffraction and single‐crystal electron diffraction in the TEM using the automated diffraction tomography (ADT) technique. The isothermal bulk modulus was determined as Bo=193(5) GPa by using in‐situ synchrotron X‐ray diffraction in a diamond anvil cell. The structure model is supported by DFT calculations. The enthalpy of formation, the bulk modulus, and the band structure have been calculated. [ABSTRACT FROM AUTHOR]

SnGe 4 N 4 O 4 was synthesized at high pressure (16 and 20 GPa) and high temperature (1200 and 1500°C) in a large-volume press. Powder X-ray diffraction experiments using synchrotron radiation indicate that the derived samples are mixtures of known and unknown phases. However, the powder X-ray diffraction patterns are not sufficient for structural characterization. Transmission electron microscopy studies reveal crystals of several hundreds of nanometres in size with different chemical composition. Among them, crystals of a previously unknown phase with stoichiometry SnGe 4 N 4 O 4 were detected and investigated using automated diffraction tomography (ADT), a three-dimensional electron diffraction method. Via ADT, the crystal structure could be determined from single nanocrystals in space group P6 3 mc, exhibiting a nolanite-type structure. This was confirmed by density functional theory calculations and atomic resolution scanning transmission electron microscopy images. In one of the syntheses runs a rhombohedral 6R polytype of SnGe 4 N 4 O 4 could be found together with the nolanite-type SnGe 4 N 4 O 4 . The structure of this polymorph was solved as well using ADT., (open access.)

We report the first oxynitride of tin, Sn 2 N 2 O (SNO), exhibiting a Rh 2 S 3 -type crystal structure with space group Pbcn. All Sn atoms are in six-fold coordination, in contrast to Si in silicon oxynitride (Si 2 N 2 O) and Ge in the isostructural germanium oxynitride (Ge 2 N 2 O), which appear in four-fold coordination. SNO was synthesized at 20 GPa and 1200-1500 °C in a large volume press. The recovered samples were characterized by synchrotron powder X-ray diffraction and single-crystal electron diffraction in the TEM using the automated diffraction tomography (ADT) technique. The isothermal bulk modulus was determined as B o =193(5) GPa by using in-situ synchrotron X-ray diffraction in a diamond anvil cell. The structure model is supported by DFT calculations. The enthalpy of formation, the bulk modulus, and the band structure have been calculated., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)