Consideration for the correlation between basicity of oxide glasses and chemical shift of O1s binding energy in XPS

Binding energy of O1s core electron measured in XPS is a candidate to determine new scale of Lewis basicity of oxide ion in glass. Some mathematical expressions for the basicity or XPS chemical shift, such as charge parameter and optical basicity, are compared with experimental O1s binding energy in binary alkali oxide glasses. The expressions so far in use need some modification in parameters. A new empirical expression introduced in this paper gives new concept and universal scale of basicity

Chemically triggered formation of two-dimensional epitaxial quantum dot superlattices

Two dimensional superlattices of epitaxially connected quantum dots enable size-quantization effects to be combined with high charge carrier mobilities, an essential prerequisite for highly performing QD devices based on charge transport. Here, we demonstrate that surface active additives known to restore nanocrystal stoichiometry can trigger the formation of epitaxial superlattices of PbSe and PbS quantum dots. More specifically, we show that both chalcogen-adding (sodium sulfide) and lead oleate displacing (amines) additives induce small area epitaxial superlattices of PbSe quantum dots. In the latter case, the amine basicity is a sensitive handle to tune the superlattice symmetry, with strong and weak bases yielding pseudohexagonal or quasi-square lattices, respectively. Through density functional theory calculations and in situ titrations monitored by nuclear magnetic resonance spectroscopy, we link this observation to the concomitantly different coordination enthalpy and ligand displacement potency of the amine. Next to that, an initial similar to 10% reduction of the initial ligand density prior to monolayer formation and addition of a mild, lead oleate displacing chemical trigger such as aniline proved key to induce square superlattices with long-range, square micrometer order; an effect that is the more pronounced the larger the quantum dots. Because the approach applies to PbS quantum dots as well, we conclude that it offers a reproducible and rational method for the formation of highly ordered epitaxial quantum dot superlattices

酸化物ガラスの塩基度と XPS による O1s 化学シフトの相関に関する考察

O1s binding energy measured by X-ray photoelectron spectroscopy (XPS) is candidate as a new tool to determine a new scale of Lewis basicity of oxide ions in glass. Some mathematical expressions for the basicity or XPS chemical shift, such as charge parameter and optical basicity, were compared with the experimental O1s binding energy in binary alkali oxide glasses. The expressions so far in use needed some modification in parameters. A new empirical expression introduced in this paper gives a new concept and universal scale of basicity

Trace element geochemistry of ordinary chondrite chondrules: the type I/type II chondrule dichotomy

We report trace element concentrations of silicate phases in chondrules from LL3 ordinary chondrites Bishunpur and Semarkona. Results are similar to previously reported data for carbonaceous chondrites, with rare earth element (REE) concentrations increasing in the sequence olivine < pyroxene < mesostasis, and heavy REE (HREE) being enriched by 1-2 orders of magnitude (CI-normalized) relative to light REE (LREE) in ferromagnesian silicates, although no single olivine with very large LREE/HREE fractionation has been found. On average, olivine in type II chondrules is poorer in refractory lithophile incompatible elements (such as REE) than its type I counterpart by a factor of ~2. This suggests that olivine in type I and II chondrules formed by batch and fractional crystallization, respectively, implying that type II chondrules formed under faster cooling rates (> ~ 10 K/h) than type I chondrules. Appreciable Na concentrations (3-221 ppm) are measured in olivine from both chondrule types; type II chondrules seem to have behaved as closed systems, which may require chondrule formation in the vicinity of protoplanets or planetesimals. At any rate, higher solid concentrations in type II chondrule forming regions may explain the higher oxygen fugacities they record compared to type I chondrules. Type I and type II chondrules formed in different environments and the correlation between high solid concentrations and/or oxygen fugacities with rapid cooling rates is a key constraint that chondrule formation models must account for.Comment: 46 pages, 7 figure