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Trisodium bismuthide (Na 3 Bi) is the first experimentally verified topological Dirac semimetal, and is a 3D analogue of graphene hosting relativistic Dirac fermions. Its unconventional momentum–energy relationship is interesting from a fundamental perspective, yielding exciting physical properties such as chiral charge carriers, the chiral anomaly, and weak anti‐localization. It also shows promise for realizing topological electronic devices such as topological transistors. Herein, an overview of the substantial progress achieved in the last few years on Na 3 Bi is presented, with a focus on technologically relevant large‐area thin films synthesized via molecular beam epitaxy. Key theoretical aspects underpinning the unique electronic properties of Na 3 Bi are introduced. Next, the growth process on different substrates is reviewed. Spectroscopic and microscopic features are illustrated, and an analysis of semiclassical and quantum transport phenomena in different doping regimes is provided. The emergent properties arising from confinement in two dimensions, including thickness‐dependent and electric‐field‐driven topological phase transitions, are addressed, with an outlook toward current challenges and expected future progress.

Progress in Epitaxial Thin‐Film Na 3 Bi as a Topological Electronic Material