In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50 Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above T g of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant.
Bibliographical noteFunding Information:
This work was supported by the Global Research Laboratory Program of the Korean Ministry of Education, Science and Technology, and the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF Grant No. 2014R1A1A1003415). Computational resources have been provided by the KISTI supercomputing center (Grant No. KSC-2014-C3-062).
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