Observation of variable hybridized-band gaps in Eu-intercalated graphene.

We report europium (Eu)-induced changes in the π-band of graphene (G) formed on the 6H-SiC(0001) surface by a combined study of photoemission measurements and density functional theory (DFT) calculations. Our photoemission data reveal that Eu intercalates upon annealing at 120 °C into the region between the graphene and the buffer layer (BL) to form a G/Eu/BL system, where a band gap of 0.29 eV opens at room temperature. This band gap is found to increase further to 0.48 eV upon cooling down to 60 K. Our DFT calculations suggest that the increased band gap originates from the enhanced hybridization of the graphene π-band with the Eu 4f band due to the increased magnetic ordering upon cooling. These Eu atoms continue to intercalate further down below the BL to produce bilayer graphene (G/BL/Eu) upon annealing at 300 °C. The π-band stemming from the BL then exhibits another band gap of 0.37 eV, which appears to be due to the strong hybridization between the π-band of the BL and the Eu 4f band. The Eu-intercalated graphene thus illustrates an example of versatile band gaps formed under different thermal treatments, which may play a critical role for future applications in graphene-based electronics.

Modification of thermal and electronic properties of bilayer graphene by using slow Na+ ions.

Bilayer graphene (BLG) has an extensive list of industrial applications in graphene-based nanodevices such as energy storage devices, flexible displays, and thermoelectric devices. By doping slow Na+ ions on Li-intercalated BLG, we find significantly improved thermal and electronic properties of BLG by using angle-resolved photoemission and high-resolution core level spectroscopy (HRCLS) with synchrotron photons. Our HRCLS data reveal that the adsorbed Na+ ions on a BLG produced by Li-intercalation through single layer graphene (SLG) spontaneously intercalate below the BLG, and substitute Li atoms to form Na-Si bonds at the SiC interface while preserving the same phase of BLG. This is in sharp contrast with no intercalation of Na+ ions on SLG though neutral Na atoms intercalate. The Na+-induced BLG is found to be stable upon heating up to T = 400 °C, but returns to SLG when heated at T d = 500 °C. The evolution of the π-bands upon doping the Na+ ions followed by thermal annealing shows that the carrier concentration of the π-band may be artificially controlled without damaging the Dirac nature of the π-electrons. The doubled desorption temperature from that (T d = 250 °C) of the Na-intercalated SLG together with the electronic stability of the Na+-intercalated BLG may find more practical and effective applications in advancing graphene-based thermoelectric devices and anode materials for rechargeable batteries.

Band gap engineering for single-layer graphene by using slow Li(+) ions.

In order to utilize the superb electronic properties of graphene in future electronic nano-devices, a dependable means of controlling the transport properties of its Dirac electrons has to be devised by forming a tunable band gap. We report on the ion-induced modification of the electronic properties of single-layer graphene (SLG) grown on a SiC(0001) substrate by doping low-energy (5 eV) Li(+) ions. We find the opening of a sizable and tunable band gap up to 0.85 eV, which depends on the Li(+) ion dose as well as the following thermal treatment, and is the largest band gap in the π-band of SLG by any means reported so far. Our Li 1s core-level data together with the valence band suggest that Li(+) ions do not intercalate below the topmost graphene layer, but cause a significant charge asymmetry between the carbon sublattices of SLG to drive the opening of the band gap. We thus provide a route to producing a tunable graphene band gap by doping Li(+) ions, which may play a pivotal role in the utilization of graphene in future graphene-based electronic nano-devices.

Topological modification of the electronic structure by Bi-bilayers lying deep inside bulk Bi2Se3.

We observe the modified surface states of an epitaxial thin film of a homologous series of (Bi2)m(Bi2Se3)n, as a topological insulator (TI), by angle-resolved photoemission spectroscopy measurements. A thin film with m : n = 1 : 3 (Bi8Se9) has been grown with Bi2 bilayers embedded every other three quintuple layers (QLs) of Bi2Se3. Despite the reduced dimension of continuous QLs due to the Bi2 heterolayers, we find that the topological surface states stem from the inverted Bi and Se states and the topologically nontrivial structures are mainly based on the prototype of 3D TI Bi2Se3 without affecting the overall topological order.

Proximity Effect Induced Electronic Properties of Graphene on Bi2Te2Se.

We report that the π-electrons of graphene can be spin-polarized to create a phase with a significant spin-orbit gap at the Dirac point (DP) using a graphene-interfaced topological insulator hybrid material. We have grown epitaxial Bi2Te2Se (BTS) films on a chemical vapor deposition (CVD) graphene. We observe two linear surface bands from both the CVD graphene notably flattened and BTS coexisting with their DPs separated by 0.53 eV in the photoemission data measured with synchrotron photons. We further demonstrate that the separation between the two DPs, Δ(D-D), can be artificially fine-tuned by adjusting the amount of Cs atoms adsorbed on the graphene to a value as small as Δ(D-D) = 0.12 eV to find any proximity effect induced by the DPs. Our density functional theory calculation shows the opening of a spin-orbit gap of ∼20 meV in the π-band, enhanced by 3 orders of magnitude from that of a pristine graphene, and a concomitant phase transition from a semimetallic to a quantum spin Hall phase when Δ(D-D) ≤ 0.20 eV. We thus present a practical means of spin-polarizing the π-band of graphene, which can be pivotal to advance graphene-based spintronics.

Persistent topological surface state at the interface of Bi2Se3 film grown on patterned graphene.

We employed graphene as a patternable template to protect the intrinsic surface states of thin films of topological insulators (TIs) from environment. Here we find that the graphene provides high-quality interface so that the Shubnikov de Haas (SdH) oscillation associated with a topological surface state could be observed at the interface of a metallic Bi2Se3 film with a carrier density higher than ∼ 10(19) cm(-3). Our in situ X-ray diffraction study shows that the Bi2Se3 film grows epitaxially in a quintuple layer-by-layer fashion from the bottom layer without any structural distortion by interfacial strain. The magnetotransport measurements including SdH oscillations stemming from multiple conductance channels reveal that the topological surface state, with the mobility as high as ∼ 0.5 m(2)/(V s), remains intact from the graphene underneath without degradation. Given that the graphene was prepatterned on arbitrary insulating substrates, the TI-based microelectronic design could be exploited. Our study thus provides a step forward to observe the topological surface states at the interface without degradation by tuning the interface between TI and graphene into a measurable current for device application.