How Important Is the Metal-Semiconductor Contact for Schottky Barrier Transistors: A Case Study on Few-Layer Black Phosphorus?

Black phosphorus (BP) is a recently rediscovered layered two-dimensional (2D) semiconductor with a direct band gap (0.35-2 eV), high hole mobility (300-5000 cm2/Vs), and transport anisotropy. In this paper, we systematically investigated the effects of metal-semiconductor interface/contacts on the performance of BP Schottky barrier transistors. First, a "clean" metal-BP contact is formed with boron nitride (BN) passivation. It is found that the contact resistance of the clean metal-BP contact is seven times less than the previously reported values. As a result, high-performance top-gate BP transistors show a record high ON-state drain current (I on) of 940 µA/µm. Second, BN tunneling barriers are formed at the source/drain contacts to help understand the abnormally high OFF-state drain current (I off) in devices with clean metal-BP contacts. This high I off is attributed to the electron tunneling current from the drain to the channel. Finally, the I on/I off of BP field-effect transistors can be significantly improved by using an asymmetric contact structure. By inserting a thin BN tunneling barrier at the drain side, I off is reduced by a factor of ∼120 with a cost of 20% reduction in I on. This case study of contacts on BP reveals the importance of understanding the metal-semiconductor contacts for 2D Schottky barrier transistors in general.

Gating electron-hole asymmetry in twisted bilayer graphene.

Electron-hole symmetry is one of the unique properties of graphene that is generally absent in most semiconductors because of the different conduction and valence band structures. Here we report on the manipulation of electron-hole symmetry in the low-energy band structure of twisted bilayer graphene, where symmetric saddle points form in the conduction and valence bands as a result of interlayer coupling. By applying a gate voltage to a twisted bilayer with a critical rotation angle, enhanced electron resonance between the two saddle points can be turned on or off, depending on the electron-hole symmetry near the saddle points. The appearance of a 2D(+) peak, a gate-tunable Raman feature found near the critical angle, indicates a reduction of Fermi velocity in the vicinity of the saddle point to/from which electrons are inelastically scattered by phonons in the round trip of the double-resonance process.

In situ observation of step-edge in-plane growth of graphene in a STEM.

It is extremely difficult to control the growth orientation of the graphene layer in comparison to Si or III-V semiconductors. Here we report a direct observation of graphene growth and domain boundary formation in a scanning transmission electron microscope, with residual hydrocarbon in the microscope chamber being used as the carbon source for in-plane graphene growth at the step-edge of bilayer graphene substrate. We show that the orientation of the growth is strongly influenced by the step-edge structure and areas grown from a reconstructed 5-7 edge are rotated by 30° with respect to the mother layer. Furthermore, single heteroatoms like Si may act as catalytic active sites for the step-edge growth. The findings provide an insight into the mechanism of graphene growth and defect reconstruction that can be used to tailor carbon nanostructures with desired properties.

Scalable graphite/copper bishell composite for high-performance interconnects.

We present the fabrication and characterizations of novel electrical interconnect test lines made of a Cu/graphite bishell composite with the graphite cap layer grown by electron cyclotron resonance chemical vapor deposition. Through this technique, conformal multilayer graphene can be formed on the predeposited Cu interconnects under CMOS-friendly conditions. The low-temperature (400 °C) deposition also renders the process unlimitedly scalable. The graphite layer can boost the current-carrying capacity of the composite structure to 10(8) A/cm(2), more than an order of magnitude higher than that of bare metal lines, and reduces resistivity of fine test lines by ∼10%. Raman measurements reveal that physical breakdown occurs at ∼680-720 °C. Modeling the current vs voltage curves up to breakdown shows that the maximum current density of the composites is limited by self-heating of the graphite, suggesting the strong roles of phonon scattering at high fields and highlighting the significance of a metal counterpart for enhanced thermal dissipation.

Twisting bilayer graphene superlattices.

Bilayer graphene is an intriguing material in that its electronic structure can be altered by changing the stacking order or the relative twist angle, yielding a new class of low-dimensional carbon system. Twisted bilayer graphene can be obtained by (i) thermal decomposition of SiC; (ii) chemical vapor deposition (CVD) on metal catalysts; (iii) folding graphene; or (iv) stacking graphene layers one atop the other, the latter of which suffers from interlayer contamination. Existing synthesis protocols, however, usually result in graphene with polycrystalline structures. The present study investigates bilayer graphene grown by ambient pressure CVD on polycrystalline Cu. Controlling the nucleation in early stage growth allows the constituent layers to form single hexagonal crystals. New Raman active modes are shown to result from the twist, with the angle determined by transmission electron microscopy. The successful growth of single-crystal bilayer graphene provides an attractive jumping-off point for systematic studies of interlayer coupling in misoriented few-layer graphene systems with well-defined geometry.

High mobility flexible graphene field-effect transistors with self-healing gate dielectrics.

A high-mobility low-voltage graphene field-effect transistor (FET) array was fabricated on a flexible plastic substrate using high-capacitance natural aluminum oxide as a gate dielectric in a self-aligned device configuration. The high capacitance of the native aluminum oxide and the self-alignment, which minimizes access resistance, yield a high current on/off ratio and an operation voltage below 3 V, along with high electron and hole mobility of 230 and 300 cm(2)/V·s, respectively. Moreover, the native aluminum oxide is resistant to mechanical bending and exhibits self-healing upon electrical breakdown. These results indicate that self-aligned graphene FETs can provide remarkably improved device performance and stability for a range of applications in flexible electronics.

Remote catalyzation for direct formation of graphene layers on oxides.

Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth.

Graphene annealing: how clean can it be?

Surface contamination by polymer residues has long been a critical problem in probing graphene's intrinsic properties and in using graphene for unique applications in surface chemistry, biotechnology, and ultrahigh speed electronics. Poly(methyl methacrylate) (PMMA) is a macromolecule commonly used for graphene transfer and device processing, leaving a thin layer of residue to be empirically cleaned by annealing. Here we report on a systematic study of PMMA decomposition on graphene and of its impact on graphene's intrinsic properties using transmission electron microscopy (TEM) in combination with Raman spectroscopy. TEM images revealed that the physisorbed PMMA proceeds in two steps of weight loss in annealing and cannot be removed entirely at a graphene susceptible temperature before breaking. Raman analysis shows a remarkable blue-shift of the 2D mode after annealing, implying an anneal-induced band structure modulation in graphene with defects. Calculations using density functional theory show that local rehybridization of carbons from sp(2) to sp(3) on graphene defects may occur in the random scission of polymer chains and account for the blue-shift of the Raman 2D mode.

Characterization of graphene grown on bulk and thin film nickel.

We report on graphene films grown by atmospheric pressure chemical vapor deposition on bulk and thin film nickel. Carbon precipitation on the polycrystalline grains is controlled by the methane concentration and substrate cooling rate. It is found that graphene grows over multiple grains, with edges terminating along the grain boundaries and with dimensions directly correlated to the size of the underlying grains. This greatly restricts the resulting graphene size (<10 µm) in the thin film growth, whereas monolayer graphene with linear dimensions of hundreds of micrometers takes up the great majority of the surface overlayers on the bulk nickel (>50%). In addition, the number of layers can be better controlled in the bulk growth. Characterizations of the graphene sheets using transmission electron microscopy, Raman spectroscopy, and transport measurements in the field-effect configuration are also discussed.