Jay Gupta

Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene

Graphenes success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in field-effect transistors, spin- and valley-tronics, thermoelectrics, and topological insulators, among many other applications.

A Single Molecule Kondo Switch: Multistability of Tetracyanoethylene on Cu(111)

Single tetracyanoethyelene (TCNE) molecules on Cu(111) are reversibly switched among five states by applying voltage pulses with the tip of a scanning tunneling microscope. A pronounced Kondo resonance in tunneling spectroscopy indicates that one of the states is magnetic. Side bands of the Kondo resonance appear at energies which correspond to inter- and intramolecular vibrational modes. Density functional theory suggests that molecular deformation changes the occupancy in TCNEs molecular orbitals, thus producing the magnetic state.

Incommensurability and atomic structure of c(2X2)N/Cu(100) : A scanning tunneling microscopy study

We use a scanning tunneling microscope operating in a low temperature, ultrahigh vacuum environment to study the atomic structure of single layer films of Cu2N grown on Cu(100). The c(2x2) lattice of Cu2N is incommensurate, with a lattice constant of 3.72 +/- 0.02 angstrom that is 3% larger than the bare Cu(100) surface. This finding suggests that strain due to lattice mismatch contributes to self assembly in this system. We find that the image contrast on Cu2N islands depends on bias voltage, which reconciles several interpretations in the literature. We assign features in these STM images to the Cu, N and hollow sites in the Cu2N lattice with the aid of co-adsorbed CO molecules. This atomic registry allows us to characterize four different defects on Cu2N, which influence the sticking coefficient and electronic coupling of adsorbates.

Tunable Control over the Ionization State of Single Mn Acceptors in GaAs with Defect-Induced Band Bending

A scanning tunneling microscope was used to study the ionization of single Mn acceptors in GaAs(110). The ionization state switches when the GaAs valence band is bent across a Mn acceptor level. This produces a ringlike feature in STM images, whose diameter depends on the tunneling conditions and distance to charged arsenic vacancies. By varying the latter, we could tune the ionization switching, as well as quantify the contributions from tip- and vacancy-induced band bending.

Magnetism in Single Metalloorganic Complexes Formed by Atom Manipulation

The magnetic properties of molecular structures can be tailored by chemical synthesis or bottom-up assembly at the atomic scale. We used scanning tunneling microscopy to study charge and spin transfer in individual complexes of transition metals with the charge acceptor, tetracyanoethylene (TCNE). The complexes were formed on a thin insulator, Cu2N on Cu(100), by manipulation of individual atoms and molecules. The Cu2N layer decouples the complexes from Cu electron density, enabling direct imaging of the TCNE molecular orbitals as well as spin-flip inelastic electron tunneling spectroscopy. Results were obtained at low temperature down to 1 K and in magnetic fields up to 7 T in order to resolve splitting of spin states in the complexes. We also performed spin-polarized density functional theory calculations to compare with the experimental data. Our results indicate that charge transfer to TCNE leads to a change in spin magnitude, Kondo resonance, and magnetic anisotropy for the metal atoms.

Room Temperature Intrinsic Ferromagnetism in Epitaxial Manganese Selenide Films in the Monolayer Limit

Monolayer van der Waals (vdW) magnets provide an exciting opportunity for exploring two-dimensional (2D) magnetism for scientific and technological advances, but the intrinsic ferromagnetism has only been observed at low temperatures. Here, we report the observation of room temperature ferromagnetism in manganese selenide (MnSe x) films grown by molecular beam epitaxy (MBE). Magnetic and structural characterization provides strong evidence that, in the monolayer limit, the ferromagnetism originates from a vdW manganese diselenide (MnSe2) monolayer, while for thicker films it could originate from a combination of vdW MnSe2 and/or interfacial magnetism of α-MnSe(111). Magnetization measurements of monolayer MnSe x films on GaSe and SnSe2 epilayers show ferromagnetic ordering with a large saturation magnetization of ∼4 Bohr magnetons per Mn, which is consistent with the density functional theory calculations predicting ferromagnetism in monolayer 1T-MnSe2. Growing MnSe x films on GaSe up to a high thickness (∼40 nm) produces α-MnSe(111) and an enhanced magnetic moment (∼2×) compared to the monolayer MnSe x samples. Detailed structural characterization by scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), and reflection high energy electron diffraction (RHEED) reveals an abrupt and clean interface between GaSe(0001) and α-MnSe(111). In particular, the structure measured by STEM is consistent with the presence of a MnSe2 monolayer at the interface. These results hold promise for potential applications in energy efficient information storage and processing.

Atomic-scale engineering of the electrostatic landscape of semiconductor surfaces.

A low-temperature scanning tunneling microscope was used in conjunction with density functional theory calculations to determine the binding sites and charge states of adsorbed Ga and Mn atoms on GaAs(110). To quantify the adatom charge states (both +1e), the Coulomb interaction with an individual Mn acceptor is measured via tunneling spectroscopy and compared with theoretical predictions. Several methods for positioning these charged adatoms are demonstrated, allowing us to engineer the electrostatic landscape of the surface with atomic precision.

Native defects in ultra-high vacuum grown graphene islands on Cu(1 1 1)

We present a scanning tunneling microscopy (STM) study of native defects in graphene islands grown by ultra-high vacuum decomposition of ethylene on Cu(1 1 1). We characterize these defects through a survey of their apparent heights, atomic-resolution imaging, and detailed tunneling spectroscopy. Bright defects that occur only in graphene regions are identified as C site point defects in the graphene lattice and are most likely single C vacancies. Dark defect types are observed in both graphene and Cu regions, and are likely point defects in the Cu surface. We also present data showing the importance of bias and tip termination to the appearance of the defects in STM images and the ability to achieve atomic resolution. Finally, we present tunneling spectroscopy measurements probing the influence of point defects on the local electronic landscape of graphene islands.

Orientation dependence of charge transfer for C60 on Cu(100)

Scanning tunneling microscopy was used to characterize the lowest unoccupied molecular orbitals (LUMO), up to LUMO+3, of individual C60 molecules within monolayer films on Cu(100). On this surface C60 orients in four distinct configurations with respect to the substrate. Tunneling spectroscopy and spectroscopic imaging were used to identify the energies and spatial distributions of the molecular orbitals. We find that the LUMO shifts by ∼200 meV depending on the orientation of the molecule, which suggests charge transfer between the surface and molecule is orientation dependent. Orientation-dependent shifts were also observed for the higher unoccupied molecular orbitals.

Modification of Electronic Surface States by Graphene Islands on Cu(111)

We present a study of graphene/substrate interactions on UHV-grown graphene islands with minimal surface contamination using \emph{in situ} low-temperature scanning tunneling microscopy (STM). We compare the physical and electronic structure of the sample surface with atomic spatial resolution on graphene islands versus regions of bare Cu(111) substrate. We find that the Rydberg-like series of image potential states is shifted toward lower energy over the graphene islands relative to Cu(111), indicating a decrease in the local work function, and the resonances have a much smaller linewidth, indicating reduced coupling to the bulk. In addition, we show the dispersion of the occupied Cu(111) Shockley surface state is influenced by the graphene layer, and both the band edge and effective mass are shifted relative to bare Cu(111).