HCl Flow-Induced Phase Change of α‑, β‑, and ε‑Ga₂O₃ Films Grown by MOCVD

Precise control of the heteroepitaxy on a low-cost foreign substrate is often the key to drive the success of fabricating semiconductor devices in scale when a large low-cost native substrate is not available. Here, we successfully synthesized three different phases of Ga₂O₃ (α, β, and ε) films on <i>c</i>-plane sapphire by only tuning the flow rate of HCl along with other precursors in an MOCVD reactor. A 3-fold increase in the growth rate of pure β-Ga₂O₃ was achieved by introducing only 5 sccm of HCl flow. With continuously increased HCl flow, a mixture of β- and ε-Ga₂O₃ was observed, until the Ga₂O₃ film transformed completely to a pure ε-Ga₂O₃ with a smooth surface and the highest growth rate (∼1 μm/h) at a flow rate of 30 sccm. At 60 sccm, we found that the film tended to have a mixture of α- and ε-Ga₂O₃ with a dominant α-Ga₂O₃, while the growth rate dropped significantly (∼0.4 μm/h). The film became rough as a result of the mixture phases since the growth rate of ε-Ga₂O₃ is much higher than that of α-Ga₂O₃. In this HCl-enhanced MOCVD mode, the Cl impurity concentration was almost identical among the investigated samples. On the basis of our density functional theory calculation, we found that the relative energy between β-, ε-, and α-Ga₂O₃ became smaller, thus inducing the phase change by increasing the HCl flow in the reactor. Thus, it is plausible that the HCl acted as a catalyst during the phase transformation process. Furthermore, we revealed the microstructure and the epitaxial relationship between Ga₂O₃ with different phases and the <i>c</i>-plane sapphire substrates. Our HCl-enhanced MOCVD approach paves the way to achieving highly controllable heteroepitaxy of Ga₂O₃ films with different phases for device applications