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

Nanomaterials (Basel). 2023 Nov 10;13(22):2925. doi: 10.3390/nano13222925.

Abstract

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.

Keywords: Al/Si; activation energy; aluminum-induced crystallization; amorphous silicon; enthalpy; kinetics; metal-induced crystallization; multilayer film; nanolayer; simultaneous thermal analysis (STA).