Jun Kawano

Needle-like grains across growth lines in the coral skeleton of Porites lobata.

The skeletal texture and crystal morphology of the massive reef-building coral Porites lobata were observed from the nano- to micrometer scale using an analytical transmission electron microscope (ATEM). The skeletal texture consists of centers of calcification (COCs) and fiber area. Fiber areas contain bundles of needle-like aragonite crystals that are elongated along the crystallographic c-axis and are several hundred nanometers to one micrometer in width and several micrometers in length. The size distribution of aragonite crystals is relatively homogeneous in the fibers. Growth lines are observed sub-perpendicular to the direction of aragonite growth. These growth lines occur in 1-2 μm intervals and reflect a periodic contrast in the thickness of an ion-spattered sample and pass through the interior of some aragonite crystals. These observations suggest that the medium filled in the calcification space maintains a CaCO₃-supersaturated state during fiber growth and that a physical change occurs periodically during the aragonite crystals of the fiber area.

The effect of Mg2+ incorporation on the structure of calcium carbonate clusters: investigation by the anharmonic downward distortion following method

Mg(2+) is considered to play an important role in the formation of calcium carbonate polymorphs; however, how it affects polymorph selection during the early stages of CaCO3 formation is not yet well understood. In the present study, in order to clarify the effect of Mg(2+) on the nucleation of calcium carbonate polymorphs, the stable structures of anhydrous additive-free and Mg-containing calcium carbonate clusters are derived using the anharmonic downward distortion following method, based on quantum chemical calculations. Optimization is performed at the B3LYP/6-31+G(d) level and the solvent effect is induced by the self-consistent reaction field method using the conductor-like polarized continuum calculation model. Calculation results show that incorporating Mg(2+) into clusters can change the clusters stable configuration. In the case of dimers and trimers, a Mg ion strongly prefers to locate at the centre of the clusters, which suggests that Mg is easy to incorporate into the clusters once it is released from its tight hydration shell. Notably, structures similar to the crystalline phase appear when only four CaCO3 units aggregate into the cluster: in the stable structure of the additive-free CaCO3 tetramer, the arrangement of Ca and CO3 ions is almost the same as that of the calcite structure, while the structure of the Mg-containing CaCO3 tetramer resembles the aragonite structure in the way that CO3 ions are stacked. These results indicate that Mg can play a key role in aragonite formation not only by inhibiting calcite growth but also by directly promoting aragonite nucleation in the early stages of CaCO3 formation.

Incorporation of Mg2+ in surface Ca2+ sites of aragonite: an ab initio study

First-principles calculations of Mg2+-containing aragonite surfaces are important because Mg2+ can affect the growth of calcium carbonate polymorphs. New calculations that incorporate Mg2+ substitution for Ca2+ in the aragonite {001} and {110} surfaces clarify the stability of Mg2+ near the aragonite surface and the structure of the Mg2+-containing aragonite surface. The results suggest that the Mg2+ substitution energy for Ca2+ at surface sites is lower than that in the bulk structure and that Mg2+ can be easily incorporated into the surface sites; however, when Mg2+ is substituted for Ca2+ in sites deeper than the second Ca2+ layer, the substitution energy approaches the value of the bulk structure. Furthermore, Mg2+ at the aragonite surface has a significant effect on the surface structure. In particular, CO3 groups rotate to achieve six-coordinate geometry when Mg2+ is substituted for Ca2+ in the top layer of the {001} surface or even in the deeper layers of the {110} surface. The rotation may relax the atomic structure around Mg2+ and reduces the substitution energy. The structural rearrangements observed in this study of the aragonite surface induced by Mg2+ likely change the stability of aragonite and affect the polymorph selection of CaCO3.

Superior solid solubility of MnSiO3 in CaSiO3 perovskite

The silicate perovskite phase relation between CaSiO3 and MnSiO3 was investigated at 35–52xa0GPa and at 1,800xa0K using laser-heated diamond anvil cells combined with angle-dispersive synchrotron X-ray diffraction and energy-dispersive X-ray spectroscopic chemical analyses with scanning or transmission electron microscopy. We found that MnSiO3 can be incorporated into CaSiO3 perovskite up to 55, and 20xa0molxa0% of CaSiO3 is soluble in MnSiO3 perovskite. The range of 55–80xa0molxa0% of MnSiO3 in the CaSiO3–MnSiO3 perovskite system could be immiscible. We also observed that the two perovskite structured phases of the Mn-bearing CaSiO3 and the Ca-bearing MnSiO3 coexisted at these conditions. The Mn-bearing CaSiO3 perovskite has non-cubic symmetry and the Ca-bearing MnSiO3 perovskite has an orthorhombic structure with space group Pbnm. All the perovskite structured phases in the CaSiO3–MnSiO3 system convert to the amorphous phase during pressure release. MnSiO3 is the first chemical component confirmed to show such a superior solid solubility in CaSiO3 perovskite.

N substitution in GaAs(001) surface under an atmosphere of hydrogen

First-principles calculations of GaAsN surface with low nitrogen (N) content grown by chemical beam epitaxy were performed to theoretically analyze the incorporation process of nitrogen and impurities at the atomic scale. As a result, stable surface structures of GaAsN(001) under hydrogen (H) atmosphere were determined. In these structures, N is suggested to readily substitute into surface sites, especially those that bond with H, compared with in the bulk. This indicates that N is incorporated into a thin film together with H. This may generate H-related defects, which may lead to the degradation of its electric properties. These defects are difficult to minimize by post-annealing processes. Therefore, the amount of H attached to the growth surface should be reduced in order to obtain high-quality crystals. The calculated surface phase diagram suggests that a condition in which the extent of the incorporation of H-related defects can be reduced exists.

Thermodynamic Analysis of Coherently Grown GaAsN/Ge: Effects of Different Gaseous Sources

Thermodynamic analysis of coherently grown GaAs1-xNx on Ge with low N content was performed to determine the relationship between solid composition and growth conditions. In this study, a new algorithm for the simulation code, which is applicable to wider combinations of gaseous sources than the traditional algorithm, was developed to determine the influence of different gaseous sources on N incorporation. Using this code, here we successfully compared two cases: one is a system using trimethylgallium (TMG), AsH3, and NH3, and the other uses dimethylhydrazine (DMHy) instead of NH3. It was found that the optimal N/As ratio of input gas in the system using DMHy was much lower than that using NH3. This shows that the newly developed algorithm could be a useful tool for analyzing the N incorporation during the vapor growth of GaAs1-xNx.