Structural Relaxation Kinetics for First and Second-Order Processes: Application to Pure Amorphous Silicon

TL;DR

This paper develops a method to extract kinetic parameters of structural relaxation in amorphous materials from calorimetry data, revealing insights into the relaxation behavior of amorphous silicon and its relation to crystallization.

Contribution

It introduces an improved analysis technique for relaxation kinetics that distinguishes between first and second-order processes, applied specifically to amorphous silicon.

Findings

Good agreement with experimental data for first-order processes

Pre-exponential rate constant varies significantly in a-Si

Analysis links relaxation kinetics to crystallization behavior

Abstract

The structural relaxation of amorphous materials is described as arising from the superposition of elementary processes with varying activation energies. We show that it is possible to obtain the kinetic parameters of these processes from differential scanning calorimetry experiments. The transformation rate is predicted for the transient decay when an isotherm is reached and for the relaxation threshold detected in partially relaxed samples. Good agreement is obtained with experiment if the individual components transform through first-order kinetics, but inconsistencies arise for second-order components. Our analysis, that improves the classical treatment by Gibbs et al.[1], allows the activation energies and the pre-exponential rate constants to be extracted independently. When applied to a-Si, we conclude that the pre-exponential rate constant is far from constant. The kinetic parameters obtained from DSC are used to analyze the relaxation of a-Si in pulsed laser experiments and to discuss the relationship between structural relaxation and crystallization.