Joaquin F. Rodriguez-Nieva

Synthesis of Monolayer Hexagonal Boron Nitride on Cu Foil Using Chemical Vapor Deposition

Hexagonal boron nitride (h-BN) is very attractive for many applications, particularly, as protective coating, dielectric layer/substrate, transparent membrane, or deep ultraviolet emitter. In this work, we carried out a detailed investigation of h-BN synthesis on Cu substrate using chemical vapor deposition (CVD) with two heating zones under low pressure (LP). Previous atmospheric pressure (AP) CVD syntheses were only able to obtain few layer h-BN without a good control on the number of layers. In contrast, under LPCVD growth, monolayer h-BN was synthesized and time-dependent growth was investigated. It was also observed that the morphology of the Cu surface affects the location and density of the h-BN nucleation. Ammonia borane is used as a BN precursor, which is easily accessible and more stable under ambient conditions than borazine. The h-BN films are characterized by atomic force microscopy, transmission electron microscopy, and electron energy loss spectroscopy analyses. Our results suggest that the growth here occurs via surface-mediated growth, which is similar to graphene growth on Cu under low pressure. These atomically thin layers are particularly attractive for use as atomic membranes or dielectric layers/substrates for graphene devices.

Raman Enhancement Effect on Two-Dimensional Layered Materials: Graphene, h-BN and MoS2

Realizing Raman enhancement on a flat surface has become increasingly attractive after the discovery of graphene-enhanced Raman scattering (GERS). Two-dimensional (2D) layered materials, exhibiting a flat surface without dangling bonds, were thought to be strong candidates for both fundamental studies of this Raman enhancement effect and its extension to meet practical applications requirements. Here, we study the Raman enhancement effect on graphene, hexagonal boron nitride (h-BN), and molybdenum disulfide (MoS2), by using the copper phthalocyanine (CuPc) molecule as a probe. This molecule can sit on these layered materials in a face-on configuration. However, it is found that the Raman enhancement effect, which is observable on graphene, hBN, and MoS2, has different enhancement factors for the different vibrational modes of CuPc, depending strongly on the surfaces. Higher-frequency phonon modes of CuPc (such as those at 1342, 1452, 1531 cm(-1)) are enhanced more strongly on graphene than that on h-BN, while the lower frequency phonon modes of CuPc (such as those at 682, 749, 1142, 1185 cm(-1)) are enhanced more strongly on h-BN than that on graphene. MoS2 demonstrated the weakest Raman enhancement effect as a substrate among these three 2D materials. These differences are attributed to the different enhancement mechanisms related to the different electronic properties and chemical bonds exhibited by the three substrates: (1) graphene is zero-gap semiconductor and has a nonpolar C-C bond, which induces charge transfer (2) h-BN is insulating and has a strong B-N bond, while (3) MoS2 is semiconducting with the sulfur atoms on the surface and has a polar covalent bond (Mo-S) with the polarity in the vertical direction to the surface. Therefore, the different Raman enhancement mechanisms differ for each material: (1) charge transfer may occur for graphene; (2) strong dipole-dipole coupling may occur for h-BN, and (3) both charge transfer and dipole-dipole coupling may occur, although weaker in magnitude, for MoS2. Consequently, this work studied the origin of the Raman enhancement (specifically, chemical enhancement) and identifies h-BN and MoS2 as two different types of 2D materials with potential for use as Raman enhancement substrates.

Creating and probing electron whispering-gallery modes in graphene

A circular route to confine electrons Physical barriers are used to confine waves. Whether it is harbor walls for sea waves, a glass disk for light, or the “whispering gallery” circular chamber walls in St. Pauls Cathedral for sound, the principle of confinement—reflection—is the same. Zhao et al. used that same principle to confine electrons in a nanoscale circular cavity in graphene. Periodic patterns within the cavity were associated with an electronic wave version of whispering gallery modes. The tunability of the cavity size may provide a route for the manipulation of electrons in graphene and similar materials. Science, this issue p. 672 A scanning probe is used to form a cavity in graphene for the confinement of electrons. The design of high-finesse resonant cavities for electronic waves faces challenges due to short electron coherence lengths in solids. Complementing previous approaches to confine electronic waves by carefully positioned adatoms at clean metallic surfaces, we demonstrate an approach inspired by the peculiar acoustic phenomena in whispering galleries. Taking advantage of graphene’s gate-tunable light-like carriers, we create whispering-gallery mode (WGM) resonators defined by circular pn junctions, induced by a scanning tunneling probe. We can tune the resonator size and the carrier concentration under the probe in a back-gated graphene device over a wide range. The WGM-type confinement and associated resonances are a new addition to the quantum electron-optics toolbox, paving the way to develop electronic lenses and resonators.

Imaging electrostatically confined Dirac fermions in graphene quantum dots

Relativistic Dirac fermions can be locally confined in nanoscale graphene quantum dots using electrostatic gating, and directly imaged using scanning tunnelling microscopy before escaping via Klein tunnelling. Electrostatic confinement of charge carriers in graphene is governed by Klein tunnelling, a relativistic quantum process in which particle–hole transmutation leads to unusual anisotropic transmission at p–n junction boundaries1,2,3,4,5. Reflection and transmission at these boundaries affect the quantum interference of electronic waves, enabling the formation of novel quasi-bound states6,7,8,9,10,11,12. Here we report the use of scanning tunnelling microscopy to map the electronic structure of Dirac fermions confined in quantum dots defined by circular graphene p–n junctions. The quantum dots were fabricated using a technique involving local manipulation of defect charge within the insulating substrate beneath a graphene monolayer13. Inside such graphene quantum dots we observe resonances due to quasi-bound states and directly visualize the quantum interference patterns arising from these states. Outside the quantum dots Dirac fermions exhibit Friedel oscillation-like behaviour. Bolstered by a theoretical model describing relativistic particles in a harmonic oscillator potential, our findings yield insights into the spatial behaviour of electrostatically confined Dirac fermions.

An on/off Berry phase switch in circular graphene resonators

Flicking the Berry phase switch When an electron completes a cycle around the Dirac point (a particular location in graphenes electronic structure), the phase of its wave function changes by π. This so-called Berry phase is tricky to observe directly in solid-state measurements. Ghahari et al. built a graphene nanostructure consisting of a central region doped with positive carriers surrounded by a negatively doped background. Scanning tunneling spectroscopy revealed sudden jumps in conductivity as the external magnetic field was increased past a threshold value. The jumps occurred when electron orbits started encompassing the Dirac point, reflecting the switch of the Berry phase from zero to π. The tunability of conductivity by such minute changes in magnetic field is promising for future applications. Science, this issue p. 845 Scanning tunneling spectroscopy reveals a transition in the character of electron orbits in a graphene nanostructure. The phase of a quantum state may not return to its original value after the system’s parameters cycle around a closed path; instead, the wave function may acquire a measurable phase difference called the Berry phase. Berry phases typically have been accessed through interference experiments. Here, we demonstrate an unusual Berry phase–induced spectroscopic feature: a sudden and large increase in the energy of angular-momentum states in circular graphene p-n junction resonators when a relatively small critical magnetic field is reached. This behavior results from turning on a π Berry phase associated with the topological properties of Dirac fermions in graphene. The Berry phase can be switched on and off with small magnetic field changes on the order of 10 millitesla, potentially enabling a variety of optoelectronic graphene device applications.

Thermionic emission and negative dI/dV in photoactive graphene heterostructures.

Transport in photoactive graphene heterostructures, originating from the dynamics of photogenerated hot carriers, is governed by the processes of thermionic emission, electron-lattice thermal imbalance, and cooling. These processes give rise to interesting photoresponse effects, in particular negative differential resistance (NDR) arising in the hot-carrier regime. The NDR effect stems from a strong dependence of electron-lattice cooling on the carrier density, which results in the carrier temperature dropping precipitously upon increasing bias. The ON-OFF switching between the NDR regime and the conventional cold emission regime, as well as the gate-controlled closed-circuit current that is present at zero bias voltage, can serve as signatures of hot-carrier dominated transport.

Role of Intertube Interactions in Double- and Triple-Walled Carbon Nanotubes

Resonant Raman spectroscopy studies are performed to access information about the intertube interactions and wall-to-wall distances in double- and triple-walled carbon nanotubes. Here, we explain how the surroundings of the nanotubes in a multiwalled system influence their radial breathing modes. Of particular interest, the innermost tubes in double- and triple-walled carbon nanotube systems are shown to be significantly shielded from environmental interactions, except for those coming from the intertube interaction with their own respective host tubes. From a comparison of the Raman results for bundled as well as individual fullerene-peapod-derived double- and triple-walled carbon nanotubes, we observe that metallic innermost tubes, when compared to their semiconducting counterparts, clearly show weaker intertube interactions. Additionally, we discuss a correlation between the wall-to-wall distances and the frequency upshifts of the radial breathing modes observed for the innermost tubes in individual double- and triple-walled carbon nanotubes. All results allow us to contemplate fundamental properties related to DWNTs and TWNTs, as for example diameter- and chirality-dependent intertube interactions. We also discuss differences in fullerene-peapod-derived and chemical vapor deposition grown double- and triple-walled systems with the focus on mechanical coupling and interference effects.

Disorder-induced double resonant Raman process in graphene

An analytical study is presented of the double resonant Raman scattering process in graphene, responsible for the D and D

Berry phase jumps and giant nonreciprocity in Dirac quantum dots

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Enhanced Thermionic-Dominated Photoresponse in Graphene Schottky Junctions

features in the Raman spectra. This work yields analytical expressions for the D and D