Precursor Selection in Hybrid Molecular Beam Epitaxy of Alkaline-Earth Stannates

TL;DR

This study investigates precursor choices in oxide molecular beam epitaxy, demonstrating that hexamethylditin effectively produces high-quality BaSnO3 films even without plasma, advancing oxide synthesis with hard-to-oxidize metals.

Contribution

It identifies HMDT as a superior precursor for BaSnO3 growth in MBE, enabling phase-pure films without plasma, which is a novel finding for oxides with high-electronegativity metals.

Findings

HMDT produces high-quality BaSnO3 films without plasma.

TMT and TET are ineffective for BaSnO3 growth.

HMDT forms tin radicals aiding oxidation process.

Abstract

One of the challenges of oxide molecular beam epitaxy (MBE) is the synthesis of oxides containing metals with high electronegativity (metals that are hard to oxidize). The use of reactive organometallic precursors can potentially address this issue. To investigate the formation of radicals in MBE, we explored three carefully chosen metal-organic precursors of tin for SnO2 and BaSnO3 growth: tetramethyltin (TMT), tetraethyltin (TET), and hexamethylditin (HMDT). All three precursors produced single-crystalline, atomically smooth, and epitaxial SnO2 (101) films on r-Al2O3 in the presence of an oxygen plasma. The study of growth kinetics revealed reaction-limited and flux-limited regimes except for TET, which also exhibited a decrease in deposition rate with increasing temperature above 800 C. Contrary to these similarities, the performance of these precursors was dramatically different for BaSnO3 growth. TMT and TET were ineffective in supplying adequate tin whereas HMDT yielded phase-pure, stoichiometric BaSnO3 films. Significantly, HMDT resulted in phase-pure and stoichiometric BaSnO3 films even without the use of an oxygen plasma (i.e., with molecular oxygen alone). These results are discussed using the ability of HMDT to form tin radicals and therefore, assisting with Sn to Sn4+ oxidation reaction. Structural and electronic transport properties of films grown using HMDT with and without oxygen plasma are compared. This study provides guideline for the choice of precursors that will enable synthesis of metal oxides containing hard-to-oxidize metals using reactive radicals in MBE.