Chemically Resolved Interface Structure of Epitaxial Graphene on SiC(0001)

Atomic-layer 2D crystals have unique properties that can be significantly modified through interaction with an underlying support. For epitaxial graphene on SiC(0001), the interface strongly influences the electronic properties of the overlaying graphene. We demonstrate a novel combination of x-ray scattering and spectroscopy for studying the complexities of such a buried interface structure. This approach employs x-ray standing wave-excited photoelectron spectroscopy in conjunction with x-ray reflectivity to produce a highly resolved chemically sensitive atomic profile for the terminal substrate bilayers, interface, and graphene layers along the SiC[0001] direction. DOI: 10.1103/PhysRevLett.111.215501 PACS numbers: 61.48.Gh, 61.05.cm, 68.49.Uv, 79.60.Ài Epitaxial graphene (EG) grown on the Si-terminated face of silicon carbide [SiC Early studies revealed that EG/SiC(0001) possesses a complex 6 p 3 Â 6 p 3R30 (6R3) reconstructed interfacial layer [10], referred to herein as the interfacial, or EG 0 , layer. This layer has significant influence on the growth, morphology, and electronic behavior of the overlaying graphene Because of the importance of the interfacial layer to the behavior of EG/SiC(0001), there have been numerous efforts to characterize its structure, including low-energy electron diffraction In this Letter we detail the structure of the interface by employing a suite of x-ray characterization techniques, including depth-sensitive XPS, x-ray standing waveenhanced XPS (XSW-XPS), and x-ray reflectivity (XRR). These tools, when employed collectively, provide the chemically specific structural information necessary to clarify previously unknown details of the EG/SiC(0001) interface. This approach ultimately enables the construction of a chemically resolved interfacial map with sub-Å resolution along the SiC[0001] direction. The XSW technique affords conventional photoelectron spectroscopy with high spatial resolution due to the influence of the XSW [here produced by the SiC(0006) Bragg reflection] on the photoabsorption process. A depiction of this phenomenon is shown i

Probing the Structure and Chemistry of Perylenetetracarboxylic Dianhydride on Graphene Before and After Atomic Layer Deposition of Alumina

The superlative electronic properties of graphene suggest its use as the foundation of next-generation integrated circuits. However, this application requires precise control of the interface between graphene and other materials, especially the metal oxides that are commonly used as gate dielectrics. Toward that end, organic seeding layers have been empirically shown to seed ultrathin dielectric growth on graphene via atomic layer deposition (ALD), although the underlying chemical mechanisms and structural details of the molecule/dielectric interface remain unknown. Here, confocal resonance Raman spectroscopy is employed to quantify the structure and chemistry of monolayers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on graphene before and after deposition of alumina with the ALD precursors trimethyl aluminum (TMA) and water. Photoluminescence measurements provide further insight into the details of the growth mechanism, including the transition between layer-by-layer growth and island formation. Overall, these results reveal that PTCDA is not consumed during ALD, thereby preserving a well-defined and passivating organic interface between graphene and deposited dielectric thin films

Self-Assembled Two-Dimensional Heteromolecular Nanoporous Molecular Arrays on Epitaxial Graphene

The development of graphene functionalization strategies that simultaneously achieve two-dimensional (2D) spatial periodicity and substrate registry is of critical importance for graphene-based nanoelectronics and related technologies. Here, we demonstrate the generation of a hydrogen-bonded molecularly thin organic heteromolecular nanoporous network on epitaxial graphene on SiC(0001) using room-temperature ultrahigh vacuum scanning tunneling microscopy. In particular, perylenetetracarboxylic diimide (PTCDI) and melamine are intermixed to form a spatially periodic 2D nanoporous network architecture with hexagonal symmetry and a lattice parameter of 3.45 ± 0.10 nm. The resulting adlayer is in registry with the underlying graphene substrate and possesses a characteristic domain size of 40–50 nm. This molecularly defined nanoporous network holds promise as a template for 2D ordered chemical modification of graphene at lengths scales relevant for graphene band structure engineering

Quantitatively Enhanced Reliability and Uniformity of High‑κ Dielectrics on Graphene Enabled by Self-Assembled Seeding Layers

The full potential of graphene in integrated circuits can only be realized with a reliable ultrathin high-κ top-gate dielectric. Here, we report the first statistical analysis of the breakdown characteristics of dielectrics on graphene, which allows the simultaneous optimization of gate capacitance and the key parameters that describe large-area uniformity and dielectric strength. In particular, vertically heterogeneous and laterally homogeneous Al₂O₃ and HfO₂ stacks grown via atomic-layer deposition and seeded by a molecularly thin perylene-3,4,9,10-tetracarboxylic dianhydride organic monolayer exhibit high uniformities (Weibull shape parameter β > 25) and large breakdown strengths (Weibull scale parameter, <i>E</i>_BD > 7 MV/cm) that are comparable to control dielectrics grown on Si substrates

Ambient-Processable High Capacitance Hafnia-Organic Self-Assembled Nanodielectrics

Ambient and solution-processable, low-leakage, high capacitance gate dielectrics are of great interest for advances in low-cost, flexible, thin-film transistor circuitry. Here we report a new hafnium oxide-organic self-assembled nanodielectric (Hf-SAND) material consisting of regular, alternating π-electron layers of 4-[[4-[bis­(2-hydroxyethyl)­amino]­phenyl]­diazenyl]-1-[4-(diethoxyphosphoryl) benzyl]­pyridinium bromide) (PAE) and HfO₂ nanolayers. These Hf-SAND multilayers are grown from solution in ambient with processing temperatures ≤150 °C and are characterized by AFM, XPS, X-ray reflectivity (2.3 nm repeat spacing), X-ray fluorescence, cross-sectional TEM, and capacitance measurements. The latter yield the largest capacitance to date (1.1 μF/cm²) for a solid-state solution-processed hybrid inorganic–organic gate dielectric, with effective oxide thickness values as low as 3.1 nm and have gate leakage <10^–7 A/cm² at ±2 MV/cm using photolithographically patterned contacts (0.04 mm²). The sizable Hf-SAND capacitances are attributed to relatively large PAE coverages on the HfO₂ layers, confirmed by X-ray reflectivity and X-ray fluorescence. Random network semiconductor-enriched single-walled carbon nanotube transistors were used to test Hf-SAND utility in electronics and afforded record on-state transconductances (5.5 mS) at large on:off current ratios (<i>I</i>_ON:<i>I</i>_OFF) of ∼10⁵ with steep 150 mV/dec subthreshold swings and intrinsic field-effect mobilities up to 137 cm²/(V s). Large-area devices (>0.2 mm²) on Hf-SAND (6.5 nm thick) achieve mA on currents at ultralow gate voltages (<1 V) with low gate leakage (<2 nA), highlighting the defect-free and conformal nature of this nanodielectric. High-temperature annealing in ambient (400 °C) has limited impact on Hf-SAND leakage densities (<10^–6 A/cm² at ±2 V) and enhances Hf-SAND multilayer capacitance densities to nearly 1 μF/cm², demonstrating excellent compatibility with device postprocessing methodologies. These results represent a significant advance in hybrid organic–inorganic dielectric materials and suggest synthetic routes to even higher capacitance materials useful for unconventional electronics