Vacancy complexes in nonequilibrium germanium-tin semiconductors

TL;DR

This study investigates vacancy-related defects in epitaxial GeSn alloys using positron annihilation spectroscopy, revealing that divacancies dominate and their structure is altered by Sn content, affecting material properties.

Contribution

It provides the first detailed analysis of vacancy complexes in GeSn alloys across different Sn contents using combined spectroscopic techniques.

Findings

Divacancies are the dominant vacancy defect in GeSn layers.

Sn content influences the structure and prevalence of vacancy clusters.

Positron lifetime decreases with increasing Sn content, indicating structural changes.

Abstract

Understanding the nature and behavior of vacancy-like defects in epitaxial GeSn metastable alloys is crucial to elucidate the structural and optoelectronic properties of these emerging semiconductors. The formation of vacancies and their complexes is expected to be promoted by the relatively low substrate temperature required for the epitaxial growth of GeSn layers with Sn contents significantly above the equilibrium solubility of 1 at.%. These defects can impact both the microstructure and charge carrier lifetime. Herein, to identify the vacancy-related complexes and probe their evolution as a function of Sn content, depth-profiled pulsed low-energy positron annihilation lifetime spectroscopy and Doppler broadening spectroscopy were combined to investigate GeSn epitaxial layers with Sn content in the 6.5-13.0 at.% range. The samples were grown by chemical vapor deposition method at temperatures between 300 and 330 {\deg}C. Regardless of the Sn content, all GeSn samples showed the same depth-dependent increase in the positron annihilation line broadening parameters, which confirmed the presence of open volume defects. The measured average positron lifetimes were the highest (380-395 ps) in the region near the surface and monotonically decrease across the analyzed thickness, but remain above 350 ps. All GeSn layers exhibit lifetimes that are 85 to 110 ps higher than the Ge reference layers. Surprisingly, these lifetimes were found to decrease as Sn content increases in GeSn layers. These measurements indicate that divacancies are the dominant defect in the as-grown GeSn layers. However, their corresponding lifetime was found to be shorter than in epitaxial Ge thus suggesting that the presence of Sn may alter the structure of divacancies. Additionally, GeSn layers were found to also contain a small fraction of vacancy clusters, which become less important as Sn content increases.