James Hone

Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene

We measured the elastic properties and intrinsic breaking strength of free-standing monolayer graphene membranes by nanoindentation in an atomic force microscope. The force-displacement behavior is interpreted within a framework of nonlinear elastic stress-strain response, and yields second- and third-order elastic stiffnesses of 340 newtons per meter (N m–1) and –690 Nm–1, respectively. The breaking strength is 42 N m–1 and represents the intrinsic strength of a defect-free sheet. These quantities correspond to a Youngs modulus of E = 1.0 terapascals, third-order elastic stiffness of D = –2.0 terapascals, and intrinsic strength of σint = 130 gigapascals for bulk graphite. These experiments establish graphene as the strongest material ever measured, and show that atomically perfect nanoscale materials can be mechanically tested to deformations well beyond the linear regime.

Atomically Thin MoS2 : A New Direct-Gap Semiconductor

The electronic properties of ultrathin crystals of molybdenum disulfide consisting of N=1,2,…,6 S-Mo-S monolayers have been investigated by optical spectroscopy. Through characterization by absorption, photoluminescence, and photoconductivity spectroscopy, we trace the effect of quantum confinement on the materials electronic structure. With decreasing thickness, the indirect band gap, which lies below the direct gap in the bulk material, shifts upwards in energy by more than 0.6 eV. This leads to a crossover to a direct-gap material in the limit of the single monolayer. Unlike the bulk material, the MoS₂ monolayer emits light strongly. The freestanding monolayer exhibits an increase in luminescence quantum efficiency by more than a factor of 10⁴ compared with the bulk material.

Boron nitride substrates for high-quality graphene electronics

Graphene devices on standard SiO(2) substrates are highly disordered, exhibiting characteristics that are far inferior to the expected intrinsic properties of graphene. Although suspending the graphene above the substrate leads to a substantial improvement in device quality, this geometry imposes severe limitations on device architecture and functionality. There is a growing need, therefore, to identify dielectrics that allow a substrate-supported geometry while retaining the quality achieved with a suspended sample. Hexagonal boron nitride (h-BN) is an appealing substrate, because it has an atomically smooth surface that is relatively free of dangling bonds and charge traps. It also has a lattice constant similar to that of graphite, and has large optical phonon modes and a large electrical bandgap. Here we report the fabrication and characterization of high-quality exfoliated mono- and bilayer graphene devices on single-crystal h-BN substrates, by using a mechanical transfer process. Graphene devices on h-BN substrates have mobilities and carrier inhomogeneities that are almost an order of magnitude better than devices on SiO(2). These devices also show reduced roughness, intrinsic doping and chemical reactivity. The ability to assemble crystalline layered materials in a controlled way permits the fabrication of graphene devices on other promising dielectrics and allows for the realization of more complex graphene heterostructures.

Anomalous Lattice Vibrations of Single- and Few-Layer MoS2

Molybdenum disulfide (MoS(2)) of single- and few-layer thickness was exfoliated on SiO(2)/Si substrate and characterized by Raman spectroscopy. The number of S-Mo-S layers of the samples was independently determined by contact-mode atomic force microscopy. Two Raman modes, E(1)(2g) and A(1g), exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be explained solely by van der Waals interlayer coupling, is attributed to Coulombic interactions and possible stacking-induced changes of the intralayer bonding. This work exemplifies the evolution of structural parameters in layered materials in changing from the three-dimensional to the two-dimensional regime.

Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide

Recent progress in large-area synthesis of monolayer molybdenum disulphide, a new two-dimensional direct-bandgap semiconductor, is paving the way for applications in atomically thin electronics. Little is known, however, about the microstructure of this material. Here we have refined chemical vapour deposition synthesis to grow highly crystalline islands of monolayer molybdenum disulphide up to 120 μm in size with optical and electrical properties comparable or superior to exfoliated samples. Using transmission electron microscopy, we correlate lattice orientation, edge morphology and crystallinity with island shape to demonstrate that triangular islands are single crystals. The crystals merge to form faceted tilt and mirror twin boundaries that are stitched together by lines of 8- and 4-membered rings. Density functional theory reveals localized mid-gap states arising from these 8-4 defects. We find that mirror twin boundaries cause strong photoluminescence quenching whereas tilt boundaries cause strong enhancement. Meanwhile, mirror twin boundaries slightly increase the measured in-plane electrical conductivity, whereas tilt boundaries slightly decrease the conductivity.

Tightly bound trions in monolayer MoS2

Two-dimensional (2D) atomic crystals, such as graphene and transition-metal dichalcogenides, have emerged as a new class of materials with remarkable physical properties. In contrast to graphene, monolayer MoS(2) is a non-centrosymmetric material with a direct energy gap. Strong photoluminescence, a current on/off ratio exceeding 10(8) in field-effect transistors, and efficient valley and spin control by optical helicity have recently been demonstrated in this material. Here we report the spectroscopic identification in a monolayer MoS(2) field-effect transistor of tightly bound negative trions, a quasiparticle composed of two electrons and a hole. These quasiparticles, which can be optically created with valley and spin polarized holes, have no analogue in conventional semiconductors. They also possess a large binding energy (~ 20 meV), rendering them significant even at room temperature. Our results open up possibilities both for fundamental studies of many-body interactions and for optoelectronic and valleytronic applications in 2D atomic crystals.

One-dimensional electrical contact to a two-dimensional material.

Better Contact Along the Edge Electrical contact to graphene is normally done with metal contacts on its flat face, where there are few strong bonding sites for the metal. Wang et al. (p. 614) encapsulated graphene with hexagonal boron nitride sheets and made metal contacts along its edge, where bonding orbitals are exposed. The resulting heterostructures had high electronic performance, with room-temperature carrier mobilities near the theoretical phonon-scattering limit. Metal contacts to graphene along its edge improve bonding and, in turn, electronic performance. Heterostructures based on layering of two-dimensional (2D) materials such as graphene and hexagonal boron nitride represent a new class of electronic devices. Realizing this potential, however, depends critically on the ability to make high-quality electrical contact. Here, we report a contact geometry in which we metalize only the 1D edge of a 2D graphene layer. In addition to outperforming conventional surface contacts, the edge-contact geometry allows a complete separation of the layer assembly and contact metallization processes. In graphene heterostructures, this enables high electronic performance, including low-temperature ballistic transport over distances longer than 15 micrometers, and room-temperature mobility comparable to the theoretical phonon-scattering limit. The edge-contact geometry provides new design possibilities for multilayered structures of complimentary 2D materials.

Frictional Characteristics of Atomically Thin Sheets

Thin Friction The rubbing motion between two surfaces is always hindered by friction, which is caused by continuous contacting and attraction between the surfaces. These interactions may only occur over a distance of a few nanometers, but what happens when the interacting materials are only that thick? Lee et al. (p. 76; see the Perspective by Müser and Shakhvorostov) explored the frictional properties of a silicon tip in contact with four atomically thin quasi–two dimensional materials with different electrical properties. For all the materials, the friction was seen to increase as the thickness of the film decreased, both for flakes supported by substrates and for regions placed above holes that formed freely suspended membranes. Placing graphene on mica, to which it strongly adheres, suppressed this trend. For these thin, weakly adhered films, out-of-plane buckling is likely to dominate the frictional response, which leads to this universal behavior. A universal trend is observed for the friction properties of thin films on weakly adhering substrates. Using friction force microscopy, we compared the nanoscale frictional characteristics of atomically thin sheets of graphene, molybdenum disulfide (MoS2), niobium diselenide, and hexagonal boron nitride exfoliated onto a weakly adherent substrate (silicon oxide) to those of their bulk counterparts. Measurements down to single atomic sheets revealed that friction monotonically increased as the number of layers decreased for all four materials. Suspended graphene membranes showed the same trend, but binding the graphene strongly to a mica surface suppressed the trend. Tip-sample adhesion forces were indistinguishable for all thicknesses and substrate arrangements. Both graphene and MoS2 exhibited atomic lattice stick-slip friction, with the thinnest sheets possessing a sliding-length–dependent increase in static friction. These observations, coupled with finite element modeling, suggest that the trend arises from the thinner sheets’ increased susceptibility to out-of-plane elastic deformation. The generality of the results indicates that this may be a universal characteristic of nanoscale friction for atomically thin materials weakly bound to substrates.

Atomically thin p–n junctions with van der Waals heterointerfaces

Semiconductor p-n junctions are essential building blocks for electronic and optoelectronic devices. In conventional p-n junctions, regions depleted of free charge carriers form on either side of the junction, generating built-in potentials associated with uncompensated dopant atoms. Carrier transport across the junction occurs by diffusion and drift processes influenced by the spatial extent of this depletion region. With the advent of atomically thin van der Waals materials and their heterostructures, it is now possible to realize a p-n junction at the ultimate thickness limit. Van der Waals junctions composed of p- and n-type semiconductors--each just one unit cell thick--are predicted to exhibit completely different charge transport characteristics than bulk heterojunctions. Here, we report the characterization of the electronic and optoelectronic properties of atomically thin p-n heterojunctions fabricated using van der Waals assembly of transition-metal dichalcogenides. We observe gate-tunable diode-like current rectification and a photovoltaic response across the p-n interface. We find that the tunnelling-assisted interlayer recombination of the majority carriers is responsible for the tunability of the electronic and optoelectronic processes. Sandwiching an atomic p-n junction between graphene layers enhances the collection of the photoexcited carriers. The atomically scaled van der Waals p-n heterostructures presented here constitute the ultimate functional unit for nanoscale electronic and optoelectronic devices.

Electrical and thermal transport properties of magnetically aligned single wall carbon nanotube films

Dense, thick films of aligned single wall carbon nanotubes and nanotube ropes have been produced by filtration/deposition from suspension in strong magnetic fields. Electrical resistivity exhibits moderate anisotropy with respect to the alignment axis, while the thermopower is the same when measured parallel or perpendicular to this axis. Both parameters have identical temperature dependencies in the two orientations. Thermal conductivity in the parallel direction exceeds 200 W/mK, within a decade of graphite.