Aluminium-induced nanocrystalline Ge formation at low temperatures

The present work contributes to establishing the role of hydrogenation and of the substrates in the aluminium-induced crystallization process of amorphous germanium layers. For such a purpose, four series of a-Ge(Al) samples, deposited under identical nominal conditions, were studied: hydrogenated samples, H-free samples, and samples deposited on crystalline silicon and on glass substrates, respectively. On purpose, the impurity concentration was kept at a doping level (10⁻⁵<[Al/Ge]<2 × 10⁻³). Furthermore, the films were submitted to isochronal cumulative thermal annealing in the 200-550 °C range. Raman scattering spectroscopy was used to characterize the crystallization process. The role of Al impurity as a precursor seed for the crystallization of a-Ge:H has been clearly established, confirming that the metal-induced crystallization (MIC) phenomenon occurs at an atomic level. Moreover, it has been found that hydrogenation and the periodic nature of the substrate play a fundamental role in the appearance of crystal seeds at low temperatures. The evolution of crystallization with annealing temperature and the analysis of the distribution of crystallite sizes indicate that the formation of crystal seeds occurs at the amorphous film-substrate interface. The importance of fourfold-coordinated aluminium as the embryo of nanocrystal formation is discussed.