Showing papers by "Mildred S. Dresselhaus published in 2015"

The renaissance of black phosphorus

Abstract: One hundred years after its first successful synthesis in the bulk form in 1914, black phosphorus (black P) was recently rediscovered from the perspective of a 2D layered material, attracting tremendous interest from condensed matter physicists, chemists, semiconductor device engineers, and material scientists. Similar to graphite and transition metal dichalcogenides (TMDs), black P has a layered structure but with a unique puckered single-layer geometry. Because the direct electronic band gap of thin film black P can be varied from 0.3 eV to around 2 eV, depending on its film thickness, and because of its high carrier mobility and anisotropic in-plane properties, black P is promising for novel applications in nanoelectronics and nanophotonics different from graphene and TMDs. Black P as a nanomaterial has already attracted much attention from researchers within the past year. Here, we offer our opinions on this emerging material with the goal of motivating and inspiring fellow researchers in the 2D materials community and the broad readership of PNAS to discuss and contribute to this exciting new field. We also give our perspectives on future 2D and thin film black P research directions, aiming to assist researchers coming from a variety of disciplines who are desirous of working in this exciting research field.

Spectral mapping of thermal conductivity through nanoscale ballistic transport

Abstract: Controlling thermal properties is central to many applications, such as thermoelectric energy conversion and the thermal management of integrated circuits. Progress has been made over the past decade by structuring materials at different length scales, but a clear relationship between structure size and thermal properties remains to be established. The main challenge comes from the unknown intrinsic spectral distribution of energy among heat carriers. Here, we experimentally measure this spectral distribution by probing quasi-ballistic transport near nanostructured heaters down to 30 nm using ultrafast optical spectroscopy. Our approach allows us to quantify up to 95% of the total spectral contribution to thermal conductivity from all phonon modes. The measurement agrees well with multiscale and first-principles-based simulations. We further demonstrate the direct construction of mean free path distributions. Our results provide a new fundamental understanding of thermal transport and will enable materials design in a rational way to achieve high performance.

Large-Area Synthesis of High-Quality Uniform Few-Layer MoTe2

Abstract: The controlled synthesis of large-area, atomically thin molybdenum ditelluride (MoTe2) crystals is crucial for its various applications based on the attractive properties of this emerging material. In this work, we developed a chemical vapor deposition synthesis to produce large-area, uniform, and highly crystalline few-layer 2H and 1T′ MoTe2 films. It was found that these two different phases of MoTe2 can be grown depending on the choice of Mo precursor. Because of the highly crystalline structure, the as-grown few-layer 2H MoTe2 films display electronic properties that are comparable to those of mechanically exfoliated MoTe2 flakes. Our growth method paves the way for the large-scale application of MoTe2 in high-performance nanoelectronics and optoelectronics.

Low-Frequency Interlayer Breathing Modes in Few-Layer Black Phosphorus

Abstract: As a new two-dimensional layered material, black phosphorus (BP) is a very promising material for nanoelectronics and optoelectronics We use Raman spectroscopy and first-principles theory to characterize and understand the low-frequency (LF) interlayer breathing modes (<100 cm–1) in few-layer BP for the first time Using a laser polarization dependence study and group theory analysis, the breathing modes are assigned to Ag symmetry Compared to the high-frequency (HF) Raman modes, the LF breathing modes are considerably more sensitive to interlayer coupling and, thus, their frequencies show a stronger dependence on the number of layers Hence, they constitute an effective means to probe both the crystalline orientation and thickness of few-layer BP Furthermore, the temperature dependence shows that in the temperature range −150 to 30 °C, the breathing modes have a weak anharmonic behavior, in contrast to the HF Raman modes that exhibit strong anharmonicity

Molecular Selectivity of Graphene-Enhanced Raman Scattering

Abstract: Graphene-enhanced Raman scattering (GERS) is a recently discovered Raman enhancement phenomenon that uses graphene as the substrate for Raman enhancement and can produce clean and reproducible Raman signals of molecules with increased signal intensity. Compared to conventional Raman enhancement techniques, such as surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS), in which the Raman enhancement is essentially due to the electromagnetic mechanism, GERS mainly relies on a chemical mechanism and therefore shows unique molecular selectivity. In this paper, we report graphene-enhanced Raman scattering of a variety of different molecules with different molecular properties. We report a strong molecular selectivity for the GERS effect with enhancement factors varying by as much as 2 orders of magnitude for different molecules. Selection rules are discussed with reference to two main features of the molecule, namely its molecular energy levels and molecular structures. In particula...

Lighting Up the Raman Signal of Molecules in the Vicinity of Graphene Related Materials

Abstract: ConspectusSurface enhanced Raman scattering (SERS) is a popular technique to detect the molecules with high selectivity and sensitivity. It has been developed for 40 years, and many reviews have been published to summarize the progress in SERS. Nevertheless, how to make the SERS signals repeatable and quantitative and how to have deeper understanding of the chemical enhancement mechanism are two big challenges. A strategy to target these issues is to develop a Raman enhancement substrate that is flat and nonmetal to replace the conventional rough and metal SERS substrate. At the same time, the newly developed substrate should have a strong interaction with the adsorbate molecules to guarantee strong chemical enhancement. The flatness of the surface allows better control of the molecular distribution and configuration, while the nonmetal surface avoids disturbance of the electromagnetic mechanism.Recently, graphene and other two-dimensional (2D) materials, which have an ideal flat surface and strong chemic...

Double resonance Raman modes in monolayer and few-layer MoTe2

Abstract: We study the second-order Raman process of mono- and few-layer ${\mathrm{MoTe}}_{2}$, by combining ab initio density functional perturbation calculations with experimental Raman spectroscopy using 532, 633, and 785 nm excitation lasers. The calculated electronic band structure and the density of states show that the resonance Raman process occurs at the $M$ point in the Brillouin zone, where a strong optical absorption occurs due to a logarithmic Van Hove singularity of the electronic density of states. The double resonance Raman process with intervalley electron-phonon coupling connects two of the three inequivalent $M$ points in the Brillouin zone, giving rise to second-order Raman peaks due to the $M$-point phonons. The calculated vibrational frequencies of the second-order Raman spectra agree with the observed laser-energy-dependent Raman shifts in the experiment.

Ab initio optimization of phonon drag effect for lower-temperature thermoelectric energy conversion

Abstract: Although the thermoelectric figure of merit zT above 300 K has seen significant improvement recently, the progress at lower temperatures has been slow, mainly limited by the relatively low Seebeck coefficient and high thermal conductivity. Here we report, for the first time to our knowledge, success in first-principles computation of the phonon drag effect—a coupling phenomenon between electrons and nonequilibrium phonons—in heavily doped region and its optimization to enhance the Seebeck coefficient while reducing the phonon thermal conductivity by nanostructuring. Our simulation quantitatively identifies the major phonons contributing to the phonon drag, which are spectrally distinct from those carrying heat, and further reveals that although the phonon drag is reduced in heavily doped samples, a significant contribution to Seebeck coefficient still exists. An ideal phonon filter is proposed to enhance zT of silicon at room temperature by a factor of 20 to ∼0.25, and the enhancement can reach 70 times at 100 K. This work opens up a new venue toward better thermoelectrics by harnessing nonequilibrium phonons.

X‐Ray Spectroscopic Investigation of Chlorinated Graphene: Surface Structure and Electronic Effects

Abstract: Chemical doping of graphene represents a powerful means of tailoring its electronic properties. Synchrotron-based X-ray spectroscopy offers an effective route to investigate the surface electronic and chemical states of functionalizing dopants. In this work, a suite of X-ray techniques is used, including near edge X-ray absorption fi ne structure spectroscopy, X-ray photoemission spectroscopy, and photoemission threshold measurements, to systematically study plasma-based chlorinated graphene on different substrates, with special focus on its dopant concentration, surface binding energy, bonding confi guration, and work function shift. Detailed spectroscopic evidence of C‐Cl bond formation at the surface of single layer graphene and correlation of the magnitude of p-type doping with the surface coverage of adsorbed chlorine is demonstrated for the fi rst time. It is shown that the chlorination process is a highly nonintrusive doping technology, which can effectively produce strongly p-doped graphene with the 2D nature and long-range periodicity of the electronic structure of graphene intact. The measurements also reveal that the interaction between graphene and chlorine atoms shows strong substrate effects in terms of both surface coverage and work function shift.

15-nm channel length MoS 2 FETs with single- and double-gate structures

Abstract: We demonstrate single- and double-gated (SG & DG) field effect transistors (FETs) with a record source-drain length (L S/D ) of 15 nm built on monolayer (t ch ∼0.7 nm) and 4-layer (t ch ∼3 nm) MoS 2 channels using monolayer graphene as the Source/Drain contacts. The best devices, corresponding to DG 4-layer MoS 2 -FETs with L S/D =15 nm, had an I on /I off in excess of 106 and a minimum subthreshold swing (SS min. ) of 90 mV/dec. at V DS =0.5 V. At L S/D =1 µm and V DS =0.5 V, SS min. =66 mV/dec., which is the best SS reported in MoS 2 FETs, indicating the high quality of the interface and the enhanced channel electrostatics.

Thermionic Emission and Negative dI/dV in Photoactive Graphene Heterostructures

Abstract: Transport in photoactive graphene heterostructures, originating from the dynamics of photogenerated hot carriers, is governed by the processes of thermionic emission, electron–lattice thermal imbalance, and cooling. These processes give rise to interesting photoresponse effects, in particular negative differential resistance (NDR) arising in the hot-carrier regime. The NDR effect stems from a strong dependence of electron–lattice cooling on the carrier density, which results in the carrier temperature dropping precipitously upon increasing bias. The ON–OFF switching between the NDR regime and the conventional cold emission regime, as well as the gate-controlled closed-circuit current that is present at zero bias voltage, can serve as signatures of hot-carrier dominated transport.

Thermionic Emission and Negative dI/dV in Photoactive Graphene Heterostructures

Abstract: Transport in photoactive graphene heterostructures, originating from the dynamics of photogenerated hot carriers, is governed by the processes of thermionic emission, electron-lattice thermal imbalance and cooling. These processes give rise to interesting photoresponse effects, in particular negative differential resistance (NDR) arising in the hot-carrier regime. The NDR effect stems from a strong dependence of electron-lattice cooling on the carrier density, which results in the carrier temperature dropping precipitously upon increasing bias. The ON-OFF switching between the NDR regime and the conventional cold emission regime, as well as the gate-controlled closed-circuit current that is present at zero bias voltage, can serve as signatures of hot-carrier dominated transport.

Canonical Quantization of Crystal Dislocation and Electron-Dislocation Scattering in an Isotropic Medium

Abstract: Crystal dislocations govern the plastic mechanical properties of materials but also affect the electrical and optical properties. However, a fundamental and quantitative quantum-mechanical theory of dislocation remains undiscovered for decades. Here we present an exactly solvable quantum field theory of dislocation, for both edge and screw dislocations in an isotropic medium by introducing a new quasiparticle "dislon". With this approach, the electron-dislocation relaxation time is studied from electron self-energy which can be reduced to classical results. Moreover, a fundamentally new type of electron energy Friedel oscillation near dislocation core is predicted, which can occur even with single electron at present. For the first time, the effect of dislocations on materials' non-mechanical properties can be studied at a full quantum field theoretical level.

Application of tungsten as a carbon sink for synthesis of large-domain uniform monolayer graphene free of bilayers/multilayers

Abstract: We have found that tungsten (W) foils can be used for controlling the carbon diffusion within copper (Cu) enclosures to synthesize large-domain bi-/multi-layer-free monolayer graphene via chemical vapor deposition. We have observed that bi-/multi-layer graphene that nucleate underneath the monolayer graphene can be selectively removed by a W foil placed inside of the Cu enclosure. Both X-ray photoelectron spectroscopy and X-ray diffraction reveal the formation of tungsten sub-carbide (W2C), suggesting the role of the W foil as a carbon sink that alters the carbon concentration inside of the enclosure. Consequently, the bi-/multi-layers appear to dissolve. Utilizing this selective removal process, we were able to demonstrate large-domain (>200 μm) monolayer graphene that is free of any bi-/multi-layers by using Cu double enclosures.

Observation of Low-Frequency Interlayer Breathing Modes in Few-Layer Black Phosphorus

Abstract: As a new two-dimensional layered material, black phosphorus (BP) is a promising material for nanoelectronics and nano-optoelectronics. We use Raman spectroscopy and first-principles theory to report our findings related to low-frequency (LF) interlayer breathing modes (<100 cm1) in few-layer BP for the first time. The breathing modes are assigned to Ag symmetry by the laser polarization dependence study and group theory analysis. Compared to the high-frequency (HF) Raman modes, the LF breathing modes are much more sensitive to interlayer coupling and thus their frequencies show much stronger dependence on the number of layers. Hence, they could be used as effective means to probe both the crystalline orientation and thickness for fewlayer BP. Furthermore, the temperature dependence study shows that the breathing modes have a harmonic behavior, in contrast to HF Raman modes which are known to exhibit anharmonicity.

Hot-carrier convection in graphene Schottky junctions

Abstract: The exposed nature of the 2D electronic states in van der Waals materials are expected to render vertical transport in heterostructures highly susceptible to interfaces. We show that a new channel for energy transport - hot carrier convection - can be engineered in graphene Schottky junctions/interfaces. In this channel, hot carriers are vertically extracted through thermionic emission of graphene hot carriers into a semiconductor, thereby cooling the graphene electronic system. Large hot carrier convective energy currents can overwhelm conventional diffusive electronic energy transport, as well as dominate over electron-lattice cooling. Crucially, hot carrier convection features strongly coupled energy and charge currents that run vertically out of the graphene plane. This yields clear experimental signatures such as large and tunable responsivities of graphene Schottky junction photodetectors with a non-monotonic temperature dependence, opening up new approaches for engineering energy transport in 2D heterostructures.

Fabrication of Carbon Nanoribbons from Carbon Nanotube Arrays

Abstract: Inter-allotropic transformations of carbon are provided using moderate conditions including alternating voltage pulses and modest temperature elevation. By controlling the pulse magnitude, small-diameter single-walled carbon nanotubes are transformed into larger-diameter single-walled carbon nanotubes, multi-walled carbon nanotubes of different morphologies, and multi-layered graphene nanoribbons.

Resonant Tunneling and Intrinsic Bistability in Twisted Graphene Structures

Abstract: We predict that vertical transport in heterostructures formed by twisted graphene layers can exhibit a unique bistability mechanism. Intrinsically bistable $I\text{\ensuremath{-}}V$ characteristics arise from resonant tunneling and interlayer charge coupling, enabling multiple stable states in the sequential tunneling regime. We consider a simple trilayer architecture, with the outer layers acting as the source and drain and the middle layer floating. Under bias, the middle layer can be either resonant or nonresonant with the source and drain layers. The bistability is controlled by geometric device parameters easily tunable in experiments. The nanoscale architecture can enable uniquely fast switching times.