Sung Joon Ahn

Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium

Smoothing Graphene Several methods have been reported for the growth of monolayer graphene into areas large enough for integration into silicon electronics. However, the electronic properties of the graphene are often degraded by grain boundaries and wrinkles. Lee et al. (p. 286, published online 3 April) showed that flat, single crystals of monolayer graphene can be grown by chemical-vapor deposition on silicon wafers covered by a germanium layer that aligns the grains. The graphene can be dry-transferred to other substrates, and the germanium layer can be reused for further growth cycles. Wafer-scale single-crystal monolayer graphene can be repeatedly grown on a hydrogen-terminated germanium (110) surface. The uniform growth of single-crystal graphene over wafer-scale areas remains a challenge in the commercial-level manufacturability of various electronic, photonic, mechanical, and other devices based on graphene. Here, we describe wafer-scale growth of wrinkle-free single-crystal monolayer graphene on silicon wafer using a hydrogen-terminated germanium buffer layer. The anisotropic twofold symmetry of the germanium (110) surface allowed unidirectional alignment of multiple seeds, which were merged to uniform single-crystal graphene with predefined orientation. Furthermore, the weak interaction between graphene and underlying hydrogen-terminated germanium surface enabled the facile etch-free dry transfer of graphene and the recycling of the germanium substrate for continual graphene growth.

Epitaxial Growth of a Single-Crystal Hybridized Boron Nitride and Graphene Layer on a Wide-Band Gap Semiconductor

Vertical and lateral heterogeneous structures of two-dimensional (2D) materials have paved the way for pioneering studies on the physics and applications of 2D materials. A hybridized hexagonal boron nitride (h-BN) and graphene lateral structure, a heterogeneous 2D structure, has been fabricated on single-crystal metals or metal foils by chemical vapor deposition (CVD). However, once fabricated on metals, the h-BN/graphene lateral structures require an additional transfer process for device applications, as reported for CVD graphene grown on metal foils. Here, we demonstrate that a single-crystal h-BN/graphene lateral structure can be epitaxially grown on a wide-gap semiconductor, SiC(0001). First, a single-crystal h-BN layer with the same orientation as bulk SiC was grown on a Si-terminated SiC substrate at 850 °C using borazine molecules. Second, when heated above 1150 °C in vacuum, the h-BN layer was partially removed and, subsequently, replaced with graphene domains. Interestingly, these graphene domains possess the same orientation as the h-BN layer, resulting in a single-crystal h-BN/graphene lateral structure on a whole sample area. For temperatures above 1600 °C, the single-crystal h-BN layer was completely replaced by the single-crystal graphene layer. The crystalline structure, electronic band structure, and atomic structure of the h-BN/graphene lateral structure were studied by using low energy electron diffraction, angle-resolved photoemission spectroscopy, and scanning tunneling microscopy, respectively. The h-BN/graphene lateral structure fabricated on a wide-gap semiconductor substrate can be directly applied to devices without a further transfer process, as reported for epitaxial graphene on a SiC substrate.

Temperature-dependent molecular conduction measured by the electrochemical deposition of a platinum electrode in a lateral configuration

Temperature-dependent current–voltage (I–V) characteristics of a molecule, 1,4-benzenedimethanethiol, was measured for 30K 100K is typically 0.11eV. For T<40K, the observed temperature independent I–V characteristics are fitted to the Fowler–Nordheim tunneling expression with barrier height of 1–2eV depending on the contact strength of samples.

Direct momentum-resolved observation of one-dimensional confinement of externally doped electrons within a single subnanometer-scale wire.

Cutting-edge research in the band engineering of nanowires at the ultimate fine scale is related to the minimum scale of nanowire-based devices. The fundamental issue at the subnanometer scale is whether angle-resolved photoemission spectroscopy (ARPES) can be used to directly measure the momentum-resolved electronic structure of a single wire because of the difficulty associated with assembling single wire into an ordered array for such measurements. Here, we demonstrated that the one-dimensional (1D) confinement of electrons, which are transferred from external dopants, within a single subnanometer-scale wire (subnanowire) could be directly measured using ARPES. Convincing evidence of 1D electron confinement was obtained using two different gold subnanowires with characteristic single metallic bands that were alternately and spontaneously ordered on a stepped silicon template, Si(553). Noble metal atoms were adsorbed at room temperature onto the gold subnanowires while the overall structure of the wires was maintained. Only one type of gold subnanowire could be controlled using external noble metal dopants without transforming the metallic band of the other type of gold subnanowires. This result was confirmed by scanning tunnelling microscopy experiments and first-principles calculations. The selective control clearly showed that externally doped electrons could be confined within a single gold subnanowire. This experimental evidence was used to further investigate the effects of the disorder induced by external dopants on a single subnanowire using ARPES.

Influence of graphene-substrate interactions on configurations of organic molecules on graphene: Pentacene/epitaxial graphene/SiC

Pentacene has been used widely in organic devices, and the interface structure between pentacene and a substrate is known to significantly influence device performances. Here we demonstrate that molecular ordering of pentacene on graphene depends on the interaction between graphene and its underlying SiC substrate. The adsorption of pentacene molecules on zero-layer and single-layer graphene, which were grown on a Sifaced 6H-SiC(0001) wafer, was studied using scanning tunneling microscopy (STM). Pentacene molecules form a quasi-amorphous layer on zero-layer graphene which interacts strongly with the underlying SiC substrate. In contrast, they form a uniformly ordered layer on the single-layer graphene having a weak graphene-SiC interaction. Furthermore, we could change the configuration of pentacene molecules on the singlelayer graphene by using STM tips. The results suggest that the molecular ordering of pentacene on graphene and the pentacene/graphene interface structure can be controlled by a graphene-substrate interaction.

Dirac electrons in a dodecagonal graphene quasicrystal

Dirac fermions in quasicrystalline graphene Quasicrystal lattices, which can have rotational order but lack translational symmetry, can be used to explore electronic properties of materials between crystals and disordered solids. Ahn et al. grew graphene bilayers rotated exactly 30° that have 12-fold rotational order. Electron diffraction and microscopy confirmed the formation of quasicrystals, and angle-resolved photoemission spectroscopy revealed anomalous interlayer electronic coupling that was quasi-periodic. The millimeter-scale layers can potentially be transferred to other substrates. Science, this issue p. 782 A Dirac fermion quasicrystal with 12-fold rotational symmetry results from twisted bilayer graphene rotated exactly 30°. Quantum states of quasiparticles in solids are dictated by symmetry. We have experimentally demonstrated quantum states of Dirac electrons in a two-dimensional quasicrystal without translational symmetry. A dodecagonal quasicrystalline order was realized by epitaxial growth of twisted bilayer graphene rotated exactly 30°. We grew the graphene quasicrystal up to a millimeter scale on a silicon carbide surface while maintaining the single rotation angle over an entire sample and successfully isolated the quasicrystal from a substrate, demonstrating its structural and chemical stability under ambient conditions. Multiple Dirac cones replicated with the 12-fold rotational symmetry were observed in angle-resolved photoemission spectra, which revealed anomalous strong interlayer coupling with quasi-periodicity. Our study provides a way to explore physical properties of relativistic fermions with controllable quasicrystalline orders.

Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalated at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.

Effects of graphene imperfections on the structure of self-assembled pentacene films

The quality of pentacene films in pentacene-based devices significantly affects their performance. In this report, the effects of various defects in graphene on a pentacene film were studied with scanning tunneling microscopy. The two most common defects found in the epitaxial graphene grown on SiC(0 0 0 1) substrates were subsurface carbon nanotube (CNT) defects and step edges. The most significant perturbation of the pentacene films was induced by step edges between single-layer and bilayer graphene domains, while the effect of step edges between single-layer domains was marginal. The subsurface CNT defects slightly distorted the structure of the single-layer pentacene, but the influence of such defects decreased as the thickness of the pentacene film increased. These results suggest that the uniformity of the graphene layer is the most important parameter in the growth of high-quality pentacene films on graphene.