Built-in Bernal gap in large-angle-twisted monolayer-bilayer graphene

Atomically thin materials offer multiple opportunities for layer-by-layer control of their electronic properties. While monolayer graphene (MLG) is a zero-gap system, Bernal-stacked bilayer graphene (BLG) acquires a finite band gap when the symmetry between the layers' potential energy is broken, usually, via a large electric field applied in double-gate devices. Here, we introduce an asymmetric twistronic stack comprising both MLG and BLG, synthesized via low-pressure chemical vapor deposition (LP-CVD) on Cu. Although a large (∼30^∘) twist angle decouples the MLG and BLG electronic bands near Fermi level, we find that the layer degeneracy in the BLG subsystem is lifted, producing a gap in the absence of external fields. The built-in interlayer asymmetry originates from proximity-induced energy shifts in the outermost layers and requires a displacement field of 0.14 V/nm to be compensated. The latter corresponds to a ∼10 meV intrinsic BLG gap, a value confirmed by our thermal-activation measurements. The present results highlight the role of structural asymmetry and encapsulating environment, expanding the engineering toolbox for monolithically-grown graphene multilayers.