Graphene is a two-dimensional material with a unique linear band structure, which gives rise to its exceptional electrical, optical, and mechanical properties.1,9-16 Its low-energy charge carriers are described as relativistic, massless Dirac fermions15, whose behavior differs significantly from that of non-relativistic charge carriers in traditional systems.15-18 Controlled deposition of a variety of impurities onto graphene provides a simple yet versatile platform for experimental studies of the response of these relativistic charge carriers to a range of perturbations. Investigations of such systems reveal that graphene impurities can shift the chemical potential6,7, alter the effective dielectric constant8, and potentially lead to electronically mediated superconductivity9. Many of these studies6-8 employ electrostatic gating as a means to tuning the properties of the hybrid impurity-graphene device. Electrostatic gating can shift the electronic structure of a material with respect to its Fermi level without hysteresis.2-5 Moreover, by tuning the charge2 or molecular5 states of such impurities, electrostatic gating can reversibly modify the properties of a hybrid impurity-graphene device.
Back-gating a graphene device provides an ideal system for investigation by scanning tunneling microscopy (STM). A scanning tunneling microscope consists of a sharp metal tip held a few angstroms away from a conductive surface. By applying a bias between the tip and the surface, electrons tunnel between the two. In the most common mode, constant current mode, one can map the topography of the sample surface by raster-scanning the tip back and forth. Additionally, the local electronic structure of the sample can be studied by examining a differential conductance dI/dV spectrum, which is proportional to local density of states (LDOS). This measurement is often termed scanning tunneling spectroscopy (STS). By separately controlling the bias and back-gate voltages, the response of graphene to impurities can be studied by analyzing the behavior of these dI/dV spectra.2-5
In this report, the fabrication of a back-gated graphene device decorated with Coulomb impurities (e.g., charged Ca atoms) is outlined. The device consists of elements in the following order (from top to bottom): calcium adatoms and clusters, graphene, hexagonal boron nitride (h-BN), silicon dioxide (SiO2), and bulk silicon (Figure 1). h-BN is an insulating thin film, which provides an atomically flat and electrically homogeneous substrate for the graphene.19-21 h-BN and SiO2 act as dielectrics, and bulk Si serves as the back-gate.
To fabricate the device, graphene is first grown on an electrochemically polished Cu foil22,23, which acts as a clean catalytic surface for the chemical vapor deposition (CVD)22-25 of graphene. In a CVD growth, methane (CH4) and hydrogen (H2) precursor gases undergo pyrolysis to form domains of graphene crystals on the Cu foil. These domains grow and eventually merge together, forming a polycrystalline graphene sheet.25 The resulting graphene is transferred onto the target substrate, an h-BN/SiO2 chip (prepared by mechanical exfoliation19-21 of h-BN onto an SiO2/Si(100) chip), via poly(methyl methacrylate) (PMMA) transfer.26-28 In the PMMA transfer, the graphene on Cu is first spin-coated with a layer of PMMA. The PMMA/graphene/Cu sample then floats on an etchant solution (e.g., FeCl3 (aq)28), which etches away the Cu. The unreacted PMMA/graphene sample is fished with an h-BN/SiO2 chip and subsequently cleaned in an organic solvent (e.g., CH2Cl2) and Ar/H2 environment29,30 to remove the PMMA layer. The resulting graphene/h-BN/SiO2/Si sample is then wire-bonded to electrical contacts on an ultra-high-vacuum (UHV) sample plate and annealed in an UHV chamber. Finally, the graphene device is deposited in situ with Coulomb impurities (e.g., charged Ca atoms) and studied by STM.2-5