Initial Optimization of the Growth Conditions of GaAs Homo-Epitaxial Layers after Cleaning and Restarting the Molecular Beam Epitaxy Reactor.

The molecular beam epitaxy (MBE) technique is renowned as the most suitable for the growth of high-quality crystalline materials and nanostructures such as GaAs. However, once established, optimal growth parameters required for repeatability of top-quality structures may be easily lost as MBE is highly sensitive to any changes in the system. Especially, routine servicing procedures, which include any activity which requires unsealing of the growth chamber, are devastating for developed growth parameters and force the necessity of recalibration. In this work, we present the process of growth parameter pre-optimization for obtaining homoepitaxial GaAs layers after servicing and restarting the MBE system. Namely, we present how each step of reestablishing optimal growth condition influences various characteristics of obtained GaAs layers. Those include in situ, structural, and spectral measurement techniques. An additional aspect was to compare the optimal conditions for the growth of homoepitaxial GaAs layers from two growth campaigns in which the main difference is the addition of an ion pump and increasing the temperature gradient on the Ga cell.

Underground radioactivity measurements of meteorites: Development of methods suitable to determine precise terrestrial age of recent falls.

The L6 chondritic meteorite, HaH-346, fell in Libya. However, neither the exact date of the fall nor the exact size of the original meteoroid or asteroid is known. A specimen of the meteorite, weighing 488 g, was measured using ultra low-background gamma-ray spectrometry in the 225 m deep underground facility HADES. Activation products 22Na, 26Al, 60Co, 57Co, 54Mn and 44Ti were detected. The detection efficiency was determined by 3D scanning the meteorite and introducing this in the computer model of the detector and sample implemented in the MCNP6.2 Monte Carlo code. The activities of 22Na and 26Al support the hypothesis that the fall took place on 26 August 2018. Furthermore, the 60Co and 26Al activities indicate that the original radius of meteoroid was between 50 and 80 cm, which suggests the mass prior to atmospheric entry was between 2400 and 7300 kg.

Charge density redistribution with pressure in a zeolite framework.

As a result of external compression applied to crystals, ions relax, in addition to shortening the bond lengths, by changing their shape and volume. Modern mineralogy is founded on spherical atoms, i.e., the close packing of spheres, ionic or atomic radii, and Pauling and Goldschmidt rules. More advanced, quantum crystallography has led to detailed quantitative studies of electron density in minerals. Here we innovatively apply it to high-pressure studies up to 4.2 GPa of the mineral hsianghualite. With external pressure, electron density redistributes inside ions and among them. For most ions, their volume decreases; however, for silicon volume increases. With growing pressure, we observed the higher contraction of cations in bonding directions, but a slighter expansion towards nonbonding directions. It is possible to trace the spatial redistribution of the electron density in ions even at the level of hundredths parts of an electron per cubic angstrom. This opens a new perspective to experimentally characterise mineral processes in the Earth's mantle. The use of diamond anvil cells with quantum crystallography offers more than interatomic distances and elastic properties of minerals. Interactions, energetic features, a branch so far reserved only to the first principle DFT calculations at ultra-high-pressures, become available experimentally.

Polar and Non-Polar Zn1-xMgxO:Sb Grown by MBE.

The article presents a systematic study of Sb-doped Zn1-xMgxO layers, with various concentrations of Mg, that were successfully grown by plasma-assisted MBE on polar a- and c-oriented and non-polar r-oriented sapphire substrates. X-ray diffraction confirmed the polar c-orientation of alloys grown on c-and a-oriented sapphire and non-polar structures grown on r-oriented substrates. A uniform depth distribution of the Sb dopant at level of 2 × 1020 cm-3 was determined by SIMS measurements. Raman spectroscopy revealed the presence of Sb-related modes in all samples. It also showed that Mg alloying reduces the compressive strain associated with Sb doping in ZnO. XPS analysis indicates that the chemical state of Sb atoms in ZnMgO is 3+, suggesting a substitutional position of SbZn, probably associated with two VZn vacancies. Luminescence and transmission spectra were measured to determine the band gaps of the Zn1-xMgxO layers. The band gap energies extracted from the transmittance measurements differ slightly for the a, c, and r substrate orientations, and the differences increase with increasing Mg content, despite identical growth conditions. The differences between the energy gaps, determined from transmission and PL peaks, are closely correlated with the Stokes shift and increase with the Mg content in the analyzed series of ZnMgO layers.

Experimental charge density of grossular under pressure - a feasibility study.

X-ray diffraction studies of crystals under pressure and quantitative experimental charge density analysis are among the most demanding types of crystallographic research. A successful feasibility study of the electron density in the mineral grossular under 1 GPa pressure conducted at the CRISTAL beamline at the SOLEIL synchrotron is presented in this work. A single crystal was placed in a diamond anvil cell, but owing to its special design (wide opening angle), short synchrotron wavelength and the high symmetry of the crystal, data with high completeness and high resolution were collected. This allowed refinement of a full multipole model of experimental electron distribution. Results are consistent with the benchmark measurement conducted without a diamond-anvil cell and also with the literature describing investigations of similar structures. Results of theoretical calculations of electron density distribution on the basis of dynamic structure factors mimic experimental findings very well. Such studies allow for laboratory simulations of processes which take place in the Earth's mantle.

Experimental observation of charge-shift bond in fluorite CaF2.

On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using an Ag source at 90 K to a resolution of 1.63 Å-1, a quantitative experimental charge density distribution has been obtained for fluorite (CaF2). The atoms-in-molecules integrated experimental charges for Ca2+ and F- ions are +1.40 e and -0.70 e, respectively. The derived electron-density distribution, maximum electron-density paths, interaction lines and bond critical points along Ca2+...F- and F-...F- contacts revealed the character of these interactions. The Ca2+...F- interaction is clearly a closed shell and ionic in character. However, the F-...F- interaction has properties associated with the recently recognized type of interaction referred to as `charge-shift' bonding. This conclusion is supported by the topology of the electron localization function and analysis of the quantum theory of atoms in molecules and crystals topological parameters. The Ca2+...F- bonded radii - measured as distances from the centre of the ion to the critical point - are 1.21 Šfor the Ca2+ cation and 1.15 Šfor the F- anion. These values are in a good agreement with the corresponding Shannon ionic radii. The F-...F- bond path and bond critical point is also found in the CaF2 crystal structure. According to the quantum theory of atoms in molecules and crystals, this interaction is attractive in character. This is additionally supported by the topology of non-covalent interactions based on the reduced density gradient.

Homodiselenacalix[4]arenes: Molecules with Unique Channelled Crystal Structures.

A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert-butyl ester groups. Single-crystal X-ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy-substituted macrocycle undergoes a single-crystal-to-single-crystal transformation during which the molecular structure changes its conformation from 1,3-alternate (loaded with THF/water) to 1,2-alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles.

SBN60, strontium-barium niobate at 100†K.

The title compound, Sr0.6Ba0.4Nb2O6 (strontium barium niobium oxide), belongs to the group of strontium-barium niobates with varying composition of Sr and Ba. Their general formula can be written as Sr x Ba1 - x Nb2O6. Below the Curie temperature, T c , these materials indicate ferroelectric properties. The Curie temperature for SBN60 is equal to 346±0.5 K so the structure is in the ferroelectric phase at the measurement temperature of 100 K. Characteristic for this family of compounds is the packing along the z-axis. The NbO6 corner-sharing octa-hedra surround three types of vacancy tunnels with penta-gonal, square and triangular shapes. The Sr(2+) ions partially occupy two unique sites, the first one located inside the penta-gon and the second one in the square tunnels. Consequently, they are situated on the mirror plane and the inter-section of two glide planes, respectively. The site inside the penta-gonal tunnel is additionally disordered so that the same position is shared by Ba(2+) and Sr(2+) ions whereas another part of the Ba(2+) ion occupies a different position (relative occupancies 0.43:0.41:0.16). One of the Nb(V) atoms and three of the O(2-) ions occupy general positions. The second Nb(V) atom is located on the inter-section of the mirror planes. Two remaining O(2-) ions are located on the same mirror plane. Only the Nb(V) atom and one of the O(2-) ions which is located on the mirror plane are not disordered. Each of the remaining O(2-) ions is split between two sites, with relative occupancies of 0.52:0.48 (O(2-) ions in general positions) and 0.64:0.36 (O(2-) ion on the mirror plane).

X-ray diffraction, FT-IR, and (13)C CP/MAS NMR structural studies of solvated and desolvated C-methylcalix[4]resorcinarene.

Solid C-methylcalix[4]resorcinarene solvated by acetonitrile and water (CAL-Me) and then modified by slow solvent evaporation (CAL-Me*) was studied using single-crystal and powder X-ray diffraction, FT-IR, and (13)C CP/MAS NMR. The CAL-Me solvate crystallizes in the monoclinic P2(1)/n space group with three CH(3)CN and two H(2)O molecules in the asymmetric part of the unit cell. The CAL-Me molecules adopt a typical crown conformation with all of the hydroxyl groups of the aryl rings oriented up and all of the methyl groups disposed down (the rccc isomeric form). The crystalline network is formed by resorcinarene, CH(3)CN, and H(2)O molecules and assembled by intermolecular hydrogen bonds and weak C-H...A or C-H...pi interactions. The desolvated CAL-Me* loses its crystalline character and becomes partly amorphous. It is devoid of CH(3)CN and deficient in water. However, the resorcinarene molecules still remain in the crown conformation supported by intramolecular hydrogen bonds, while intermolecular hydrogen bonds are considerably disintegrated. The work directs general attention to the problem of stability and polymorphism of resorcinarene solvates. It shows that the joint use of diffractometric and spectroscopic methods is advantageous in the structural studies of complex crystalline macromolecular systems. On the other hand, the solid-state IR and NMR spectroscopic analyses applied in tandem have been found highly beneficial to elucidate the disordered structure of poorly crystalline, desolvated resorcinarene.