Thermokinetic Study of Aluminum-Induced Crystallization of a-Si: The Effect of Al Layer Thickness.

The effect of the aluminum layer on the kinetics and mechanism of aluminum-induced crystallization (AIC) of amorphous silicon (a-Si) in (Al/a-Si)n multilayered films was studied using a complex of in situ methods (simultaneous thermal analysis, transmission electron microscopy, electron diffraction, and four-point probe resistance measurement) and ex situ methods (X-ray diffraction and optical microscopy). An increase in the thickness of the aluminum layer from 10 to 80 nm was found to result in a decrease in the value of the apparent activation energy Ea of silicon crystallization from 137 to 117 kJ/mol (as estimated by the Kissinger method) as well as an increase in the crystallization heat from 12.3 to 16.0 kJ/(mol Si). The detailed kinetic analysis showed that the change in the thickness of an individual Al layer could lead to a qualitative change in the mechanism of aluminum-induced silicon crystallization: with the thickness of Al ≤ 20 nm. The process followed two parallel routes described by the n-th order reaction equation with autocatalysis (Cn-X) and the Avrami-Erofeev equation (An): with an increase in the thickness of Al ≥ 40 nm, the process occurred in two consecutive steps. The first one can be described by the n-th order reaction equation with autocatalysis (Cn-X), and the second one can be described by the n-th order reaction equation (Fn). The change in the mechanism of amorphous silicon crystallization was assumed to be due to the influence of the degree of Al defects at the initial state on the kinetics of the crystallization process.

Solid-State Reaction in Cu/a-Si Nanolayers: A Comparative Study of STA and Electron Diffraction Data.

The kinetics of the solid-state reaction between nanolayers of polycrystalline copper and amorphous silicon (a-Si) has been studied in a Cu/a-Si thin-film system by the methods of electron diffraction and simultaneous thermal analysis (STA), including the methods of differential scanning calorimetry (DSC) and thermogravimetry (TG). It has been established that, in the solid-state reaction, two phases are formed in a sequence: Cu + Si → η″-Cu3Si → γ-Cu5Si. It has been shown that the estimated values of the kinetic parameters of the formation processes for the phases η″-Cu3Si and γ-Cu5Si, obtained using electron diffraction, are in good agreement with those obtained by DSC. The formation enthalpy of the phases η″-Cu3Si and γ-Cu5Si has been estimated to be: ΔHη″-Cu3Si = -12.4 ± 0.2 kJ/mol; ΔHγ-Cu5Si = -8.4 ± 0.4 kJ/mol. As a result of the model description of the thermo-analytical data, it has been found that the process of solid-state transformations in the Cu/a-Si thin-film system under study is best described by a four-stage kinetic model R3 → R3 → (Cn-X) → (Cn-X). The kinetic parameters of formation of the η″-Cu3Si phase are the following: Ea = 199.9 kJ/mol, log(A, s-1) = 20.5, n = 1.7; and for the γ-Cu5Si phase: Ea = 149.7 kJ/mol, log(A, s-1) = 10.4, n = 1.3, with the kinetic parameters of formation of the γ-Cu5Si phase being determined for the first time.

Formation of bimetallic Au-Pd and Au-Pt nanoparticles under hydrothermal conditions and microwave irradiation.

The reduction of chlorocomplexes of gold(III) from muriatic solutions by nanocrystal powders of palladium and platinum at 110 and 130 °C under hydrothermal conditions and the action of microwave irradiation has been investigated. The structure and composition of the solid phase have been characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and chemical methods. Bimetallic particles with a core-shell structure have been revealed. The obtained particles are established to have a core of the metal reductant covered with a substitutional solid (Au, Pd) solution in case of palladium, and isolated by a gold layer in the case of platinum. The main reason for such a difference is the ratio between the rates of aggregation and reduction. It has been shown by the example of the Au-Pd system that the use of microwave irradiation allows us not only to accelerate the synthesis of particles but also to obtain more homogeneous materials in comparison with conventional heating.

X-ray diffraction structure analysis of MCM-48 mesoporous silica.

The structure of MCM-48 mesoporous silicate materials has been fully characterized from X-ray diffraction data by applying recently developed methods of mesostructure analysis and full-profile refinement. The pore wall thickness of both as-made and calcined MCM-48 was determined with high precision to be 8.0(1) Angstrom. No regular variations of the wall thickness were detected, but its density was found to be ca. 10% higher in the low-curvature regions. The surfactant density in the pores was assessed around 0.6-0.7 g/cm(3) and was found to have a distinct minimum in the pore center similar to that detected previously in MCM-41. A new extended model function of the density distribution in MCM-48 is proposed on the basis of the structural features that were revealed.