*Correspondence to: a.khajetoorians@science.ru.nlWe report on the structural and electronic properties of a single bismuth layer intercalated underneath a graphene layer grown on an Ir(111) single crystal. Scanning tunneling microscopy (STM) reveals a hexagonal surface structure and a dislocation network upon Bi intercalation, which we attribute to a √3 × √3 R30 ∘ Bi structure on the underlying Ir(111) surface. Ab-initio calculations show that this Bi structure is the most energetically favorable, and also illustrate that STM measurements are most sensitive to C atoms in close proximity to intercalated Bi atoms.Additionally, Bi intercalation induces a band gap ( g = 0.42 eV) at the Dirac point of graphene 2 and an overall n-doping (~0.39 eV), as seen in angular-resolved photoemission spectroscopy.We attribute the emergence of the band gap to the dislocation network which forms favorably along certain parts of the moiré structure induced by the graphene/Ir(111) interface. by the structural confinement in graphene nanoribbons 9 10 ; by the stacking of multiple graphene layers 11,12 ; by the periodic modulation of the graphene lattice (breaking the sub-lattice symmetry), which can be achieved by using patterned substrates 13 , or through the patterned adsorption of other elements such as hydrogen 5 .Pristine graphene shows weak spin-orbit interactions 14 , but increasing the strength of these interactions could give rise to new interesting possibilities in spin-based nanoelectronics. One route toward manipulation of graphene's electronic structure is intercalation of defined The Ir(111) surface was cleaned in ultra-high vacuum (UHV) by repeated cycles of Ar sputtering, followed by annealing to 1470 K. Additionally, carbon contamination was removed, when necessary, by intermittent annealing in O 2 . A monolayer (ML) of high quality graphene was grown by exposing the clean Ir(111) surface to ethylene gas at a surface temperature of 1075 K. The growth process was followed by a short (< 30 ) rapid heating to max = 1455 K.This step increases the quality of the resulting graphene ML. Bismuth was subsequently deposited on the G/Ir(111) surface at a sample temperature of 715 K. After the deposition, the 5 sample was heated to a temperature of 1273 K for 60 s. This step leads to intercalated bismuth underneath the graphene. These surface regions where this intercalation structure is present are referred to as G/Bi/Ir throughout the text.Scanning tunneling microscopy (STM) was performed using a home-built variable temperature STM in a UHV system with a base pressure below 1 × 10 −10 mbar 20 21 . Tip and sample were cooled to = 30 K. Electrochemically etched and flashed W tips were used for all STM measurements. STM topography was recorded in constant current mode ( t ) with the bias applied to the sample ( S ). Differential conductance maps (short I/ V maps) were recorded by applying a modulation voltage ( mod ) using lock-in detection at a modulation frequency of = 5.477 kHz.ARPES data were acquired at the SGM3 beamline at ...