Justice M. P. Alaboson

Seeding Atomic Layer Deposition of High-k Dielectrics on Epitaxial Graphene with Organic Self-Assembled Monolayers

The development of high-performance graphene-based nanoelectronics requires the integration of ultrathin and pinhole-free high-k dielectric films with graphene at the wafer scale. Here, we demonstrate that self-assembled monolayers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) act as effective organic seeding layers for atomic layer deposition (ALD) of HfO(2) and Al(2)O(3) on epitaxial graphene on SiC(0001). The PTCDA is deposited via sublimation in ultrahigh vacuum and shown to be highly ordered with low defect density by molecular-resolution scanning tunneling microscopy. Whereas identical ALD conditions lead to incomplete and rough dielectric deposition on bare graphene, the chemical functionality provided by the PTCDA seeding layer yields highly uniform and conformal films. The morphology and chemistry of the dielectric films are characterized by atomic force microscopy, ellipsometry, cross-sectional scanning electron microscopy, and X-ray photoelectron spectroscopy, while high-resolution X-ray reflectivity measurements indicate that the underlying graphene remains intact following ALD. Using the PTCDA seeding layer, metal-oxide-graphene capacitors fabricated with a 3 nm Al(2)O(3) and 10 nm HfO(2) dielectric stack show high capacitance values of ∼700 nF/cm(2) and low leakage currents of ∼5 × 10(-9) A/cm(2) at 1 V applied bias. These results demonstrate the viability of sublimated organic self-assembled monolayers as seeding layers for high-k dielectric films in graphene-based nanoelectronics.

Fundamental Performance Limits of Carbon Nanotube Thin-Film Transistors Achieved Using Hybrid Molecular Dielectrics

In the past decade, semiconducting carbon nanotube thin films have been recognized as contending materials for wide-ranging applications in electronics, energy, and sensing. In particular, improvements in large-area flexible electronics have been achieved through independent advances in postgrowth processing to resolve metallic versus semiconducting carbon nanotube heterogeneity, in improved gate dielectrics, and in self-assembly processes. Moreover, controlled tuning of specific device components has afforded fundamental probes of the trade-offs between materials properties and device performance metrics. Nevertheless, carbon nanotube transistor performance suitable for real-world applications awaits understanding-based progress in the integration of independently pioneered device components. We achieve this here by integrating high-purity semiconducting carbon nanotube films with a custom-designed hybrid inorganic-organic gate dielectric. This synergistic combination of materials circumvents conventional design trade-offs, resulting in concurrent advances in several transistor performance metrics such as transconductance (6.5 μS/μm), intrinsic field-effect mobility (147 cm(2)/(V s)), subthreshold swing (150 mV/decade), and on/off ratio (5 × 10(5)), while also achieving hysteresis-free operation in ambient conditions.

Self-Assembly and Photopolymerization of Sub-2 nm One-Dimensional Organic Nanostructures on Graphene

While graphene has attracted significant attention from the research community due to its high charge carrier mobility, important issues remain unresolved that prevent its widespread use in technologically significant applications such as digital electronics. For example, the chemical inertness of graphene hinders integration with other materials, and the lack of a bandgap implies poor switching characteristics in transistors. The formation of ordered organic monolayers on graphene has the potential to address each of these challenges. In particular, functional groups incorporated into the constituent molecules enable tailored chemical reactivity, while molecular-scale ordering within the monolayer provides sub-2 nm templates with the potential to tune the electronic band structure of graphene via quantum confinement effects. Toward these ends, we report here the formation of well-defined one-dimensional organic nanostructures on epitaxial graphene via the self-assembly of 10,12-pentacosadiynoic acid (PCDA) in ultrahigh vacuum (UHV). Molecular resolution UHV scanning tunneling microscopy (STM) images confirm the one-dimensional ordering of the as-deposited PCDA monolayer and show domain boundaries with symmetry consistent with the underlying graphene lattice. In an effort to further stabilize the monolayer, in situ ultraviolet photopolymerization induces covalent bonding between neighboring PCDA molecules in a manner that maintains one-dimensional ordering as verified by UHV STM and ambient atomic force microscopy (AFM). Further quantitative insights into these experimental observations are provided by semiempirical quantum chemistry calculations that compare the molecular structure before and after photopolymerization.

Identifying and characterizing epitaxial graphene domains on partially graphitized SiC(0001) surfaces using scanning probe microscopy

Scanning tunneling microscopy (STM), atomic force microscopy (AFM), lateral force microscopy (LFM), and conductive AFM (cAFM) are employed to characterize epitaxial graphene on SiC(0001). Of particular interest are substrates that possess single-layer and bilayer graphene domains, which form during thermal decomposition of silicon from SiC(0001). Since these samples are often partially graphitized, characterization techniques are needed that can distinguish domains of epitaxial graphene from the adjacent (6√3×6√3)R30° reconstructed SiC(0001) surface. The relative merits of STM, AFM, LFM, and cAFM for this purpose are outlined, thus providing nanometer-scale strategies for identifying and characterizing epitaxial graphene.

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, E(BD) > 7 MV/cm) that are comparable to control dielectrics grown on Si substrates.

Templating Sub-10 nm Atomic Layer Deposited Oxide Nanostructures on Graphene via One-Dimensional Organic Self-Assembled Monolayers

Molecular-scale control over the integration of disparate materials on graphene is a critical step in the development of graphene-based electronics and sensors. Here, we report that self-assembled monolayers of 10,12-pentacosadiynoic acid (PCDA) on epitaxial graphene can be used to template the reaction and directed growth of atomic layer deposited (ALD) oxide nanostructures with sub-10 nm lateral resolution. PCDA spontaneously assembles into well-ordered domains consisting of one-dimensional molecular chains that coat the entire graphene surface in a manner consistent with the symmetry of the underlying graphene lattice. Subsequently, zinc oxide and alumina ALD precursors are shown to preferentially react with the functional moieties of PCDA, resulting in templated oxide nanostructures. The retention of the original one-dimensional molecular ordering following ALD is dependent on the chemical reaction pathway and the stability of the monolayer, which can be enhanced via ultraviolet-induced molecular cross-linking.

Conductive Atomic Force Microscope Nanopatterning of Epitaxial Graphene on SiC(0001) in Ambient Conditions

Graphene has attracted signifi cant attention in recent years for its extraordinary electronic, physical, optical, and magnetic properties. [ 1 ] In particular, epitaxial graphene (EG) grown on SiC substrates is a promising route towards realizing graphenebased electronics. [ 2–4 ] Control over the surface chemistry [ 5 , 6 ] and lithographic engineering of graphene are required for the fabrication of a wide range of devices and for incorporation with different electronic materials such as high-k dielectrics. [ 7 , 8 ]

Metal Oxide Nanoparticle Growth on Graphene via Chemical Activation with Atomic Oxygen

Chemically interfacing the inert basal plane of graphene with other materials has limited the development of graphene-based catalysts, composite materials, and devices. Here, we overcome this limitation by chemically activating epitaxial graphene on SiC(0001) using atomic oxygen. Atomic oxygen produces epoxide groups on graphene, which act as reactive nucleation sites for zinc oxide nanoparticle growth using the atomic layer deposition precursor diethyl zinc. In particular, exposure of epoxidized graphene to diethyl zinc abstracts oxygen, creating mobile species that diffuse on the surface to form metal oxide clusters. This mechanism is corroborated with a combination of scanning probe microscopy, Raman spectroscopy, and density functional theory and can likely be generalized to a wide variety of related surface reactions on graphene.