Structure Elucidation of Complex Endotaxially Intergrown Lanthanum Barium Oxonitridosilicate Oxides by Combination of Microfocused Synchrotron Radiation and Transmission Electron Microscopy.

Single-crystalline domains in intergrown microcrystalline material of the new compounds Ba22.5+x La55-x [Si129 N240-x Ox ]O3 :Ce3+ and Ba25.5+x La77-x [Si170 N312-x O9+x ]O4 :Ce3+ were identified by transmission electron microscopy (TEM). Precise diffraction data from these domains were collected with microfocused synchrotron radiation so that crystal structure elucidation of the complex disordered networks became possible. They are composed of two different interconnected slabs of which one is similar in both compounds, which explains their notorious intergrowth. The distribution of Ba and La is indicated by the analysis of bond-valence sums and by comparison with isostructural Sr28.5+x La75-x [Si170 N312-x O9+x ]O4 . Ce3+ doping leads to yellow luminescence. This is a showcase that highlights the discovery and accurate characterization of new compounds relevant for luminescence applications from heterogeneous microcrystalline samples by exploiting the capability of the combination of TEM and diffraction using the latest focusing techniques for synchrotron radiation.

Highly Symmetric AB2 Framework Related to Tridymite in the Disordered Nitridosilicate La24Sr14-7x[Si36N72](O1-xFx)14 (x = 0.489).

La24Sr14-7x[Si36N72](O1-xFx)14 with x = 0.489 was obtained as a microcrystalline product by metathesis at 1500 °C in a radio-frequency furnace starting from Si(NH)2, La(NH2)3, SrH2, LaF3, and CeF3. The structure of the new nitridosilicate oxide fluoride was determined by combining transmission electron microscopy (TEM) and single-crystal X-ray diffraction using a microfocused synchrotron beam. The structure model with pronounced disorder [P63/mmc, Z = 1, a = 16.2065(3), c = 9.4165(1) Å, R1(obs) = 0.0436] was confirmed by electron diffraction and aberration-corrected Z-contrast scanning TEM. The highly symmetric AB2 framework, which was theoretically predicted but not yet realized, consists of all-side vertex-sharing SiN4 tetrahedra that form channels along [001] filled with La, Sr, O, and F atoms. The connectivity pattern is related to that of tridymite. X-ray spectroscopy and bond-valence-sum calculations were further taken into account for assignment of the N, O, and F atoms.

From Minor Side Phases to Bulk Samples of Lanthanum Oxonitridosilicates: An Investigation with Microfocused Synchrotron Radiation.

Microcrystals of the oxonitridosilicate oxide La(11)Si(13)N(27.636)O(1.046):Ce(3+) were obtained by exploratory high-temperature synthesis starting from La, La(NH2)3, Si(NH)2, BaH2, and CeF3. Owing to the small size of the crystals, microfocused synchrotron radiation was used for structure investigations (space group Cmc21 (No. 36), a = 9.5074(4) Å, b = 32.0626(9) Å, c = 18.5076(8) Å, Z = 8, R1(all) = 0.0267). The crystal structure consists of an unprecedented interrupted three-dimensional network of vertex-sharing SiN(4-x)O(x) tetrahedra that form channels of siebener rings along [100]. Moreover, the structure is characterized by layers of condensed sechser rings in a boat conformation and vierer rings, which are alternatingly stacked with layers of vierer and dreier rings. Several split positions indicate two different local structure variants. Infrared spectroscopy confirms the absence of N-H bonds. Powder X-ray diffraction data show that bulk samples contain only a small amount of La(11)Si(13)N(27.636)O1.046:Ce(3+). However, once the exact composition was determined from structure analysis, it was possible to optimize the synthesis using fluorides as starting materials. Thereby, bulk samples of the homeotypic compound La(11)Si(13)N(27.376)O(0.936)F were obtained and investigated.

La6Ba3[Si17N29O2]Cl­An Oxonitridosilicate Chloride with Exceptional Structural Motifs.

The oxonitridosilicate chloride La6Ba3[Si17N29O2]Cl was synthesized by a high-temperature reaction in a radiofrequency furnace starting from LaCl3, BaH2, and the ammonolysis product of Si2Cl6. Diffraction data of a micrometer-sized single crystal were obtained using microfocused synchrotron radiation at beamline ID11 of the ESRF. EDX measurements on the same crystal confirm the chemical composition. The crystal structure [space group P63/m (no. 176), a = 9.8117(14), c = 19.286(6) Å, Z = 2] contains an unprecedented interrupted three-dimensional network of vertex-sharing SiN4 and SiN3O tetrahedra. The SiN4 tetrahedra form dreier rings. Twenty of the latter condense in a way that the Si atoms form icosahedra. Each icosahedron is connected to others via six SiN4 tetrahedra that are part of dreier rings and via six Q(3)-type SiN3O tetrahedra. Rietveld refinements confirm that the final product contains only a small amount of impurities. Lattice energy (MAPLE) and bond-valence sum (BVS) calculations show that the structure is electrostatically well balanced. Infrared spectroscopy confirms the absence of N-H bonds.

Increasing crystallinity for improved electrical conductivity of TiO2 blocking layers.

In this Research Article, we present our results on the optimization of the TiO2 blocking layer to improve the efficiency of organic and hybrid solar cells and make them more competitive with standard silicon devices. The major aim of the present work is to increase the electrical conductivity within the TiO2 blocking layer to guarantee for efficient charge carrier transport and separation. This is realized by optimizing the calcination processes toward an increase in particle/domain size to increase the unpercolated pathways for charge carriers and to get deeper insight into the morphology of the sol-gel produced films.