Engineering topics
Publications and source records attributed to Dresselhaus, Mildred S..
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.
Electron–phonon coupling in two-dimensional nanomaterials plays a fundamental role in determining their physical properties. Such interplay is particularly intriguing in semiconducting black phosphorus (BP) due to the highly anisotropic nature of its electronic structure and phonon dispersions. Here we report the direct observation of symmetry-dependent electron–phonon coupling in BP by performing the polarization-selective resonance Raman measurement in the visible and ultraviolet regimes, focusing on the out-of-plane A g 1 and in-plane A g 2 phonon modes. Their intrinsic resonance Raman excitation profiles (REPs) were extracted and quantitatively compared. The in-plane A g 2 mode exhibits remarkably strong resonance enhancement across the excitation wavelengths when the excitation polarization is parallel to the armchair (A g 2 //AC) direction. In contrast, a dramatically weak resonance effect was observed for the same mode with the polarization parallel to zigzag (A g 2 //ZZ) direction and for the out-of-plane A g 1 mode (A g 1 //AC and A g 1 //ZZ). Analysis on quantum perturbation theory and first-principles calculations on the anisotropic electron distributions in BP demonstrated that electron–phonon coupling considering the symmetry of the involved excited states and phonon vibration patterns is responsible for this phenomenon. Further analysis of the polarization-dependent REPs for A g phonons allows us to resolve the existing controversies on the physical origin of Raman anomaly in BP and its dependence on excitation energy, sample thickness, phonon modes, and crystalline orientation. Finally, our study gives deep insights into the underlying interplay between electrons and phonons in BP and paves the way for manipulating the electron–phonon coupling in anisotropic nanomaterials for future device applications.
Despite the established knowledge that crystal dislocations can affect a material’s superconducting properties, the exact mechanism of the electron-dislocation interaction in a dislocated superconductor has long been missing. Being a type of defect, dislocations are expected to decrease a material’s superconducting transition temperature (T c ) by breaking the coherence. Yet experimentally, even in isotropic type I superconductors, dislocations can either decrease, increase, or have little influence on T c . These experimental findings have yet to be understood. Although the anisotropic pairing in dirty superconductors has explained impurity-induced T c reduction, no quantitative agreement has been reached in the case a dislocation given its complexity. By generalizing the one-dimensional quantized dislocation field to three dimensions, we reveal that there are indeed two distinct types of electron-dislocation interactions. Besides the usual electron-dislocation potential scattering, there is another interaction driving an effective attraction between electrons that is caused by dislons, which are quantized modes of a dislocation. The role of dislocations to superconductivity is thus clarified as the competition between the classical and quantum effects, showing excellent agreement with existing experimental data. In particular, the existence of both classical and quantum effects provides a plausible explanation for the illusive origin of dislocation-induced superconductivity in semiconducting PbS/PbTe superlattice nanostructures. A quantitative criterion has been derived, in which a dislocated superconductor with low elastic moduli and small electron effective mass and in a confined environment is inclined to enhance T c . This provides a new pathway for engineering a material’s superconducting properties by using dislocations as an additional degree of freedom.
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Understanding thermal transport in lithium intercalated layered materials is not only important for managing heat generation and dissipation in lithium ion batteries but also the understanding potentially provides a novel way to design materials with reversibly tunable thermal conductivity. In this work, the thermal conductivity of lithium–graphite intercalation compounds (Li x C 6 ) is calculated using molecular dynamics simulations as a function of the amount of lithium intercalated. We found that intercalation of lithium has an anisotropic effect on tuning the thermal conductivity: the thermal conductivity in the basal plane decreases monotonically from 1232 W/m·K of pristine graphite to 444 W/m·K of the fully lithiated LiC 6 , while the thermal conductivity along the c-axis decreases first from 6.5 W/m·K for graphite to 1.3 W/m·K for LiC 18 and then increases to 5.0 W/m·K for LiC 6 as the lithium composition increases. More importantly, we provide the very first atomic-scale insight into the effect of lithium intercalation on the spectral phonon properties of graphite. The intercalated lithium ions are found to suppress the phonon lifetime and to reduce the group velocity of phonons parallel to the basal plane but significantly to increase the phonon group velocity along the c-axis, which anisotropically tunes the thermal conductivity of lithiated graphite compounds. This work could shed some light on the search for tunable thermal conductivity materials and might have strong impacts on the thermal management of lithium ion batteries.
Van der Waals (vdW) heterostructures consist of isolated atomic planar structures, assembled layer- by-layer into desired structures in a well-defined sequence. Graphene deposited on hexagonal boron nitride (h-BN) has been first considered as a testbed system for vdW heterostructures, and many others have been demonstrated both theoretically and experimentally, revealing many attractive properties and phenomena. However, much less emphasis has been placed on how graphene actively affects h-BN properties. Here, we perform local probe measurements on single-layer h-BN grown over graphene and highlight the manifestation of a proximity effect that significantly affects the electronic properties of h-BN due to its coupling with the underlying graphene. We find electronic states originating from the graphene layer and the Cu substrate to be injected into the wide electronic gap of the h-BN top layer. Such proximity effect is further confirmed in a study of the variation of h-BN in-gap states with interlayer couplings, elucidated using a combination of topographical/ spectroscopic measurements and first-principles density functional theory calculations. In conclusion, the findings of this work indicate the potential of mutually engineering electronic properties of the components of vdW heterostructures.
Layered gallium telluride (GaTe) has attracted much attention recently, due to its extremely high photoresponsivity, short response time, and promising thermoelectric performance. Different from most commonly studied two-dimensional (2D) materials, GaTe has in-plane anisotropy and a low symmetry with the C 2h 3 space group. Investigating the in-plane optical anisotropy, including the electron–photon and electron–phonon interactions of GaTe is essential in realizing its applications in optoelectronics and thermoelectrics. In this work, the anisotropic light-matter interactions in the low-symmetry material GaTe are studied using anisotropic optical extinction and Raman spectroscopies as probes. Our polarized optical extinction spectroscopy reveals the weak anisotropy in optical extinction spectra for visible light of multilayer GaTe. Polarized Raman spectroscopy proves to be sensitive to the crystalline orientation of GaTe, and shows the intricate dependences of Raman anisotropy on flake thickness, photon and phonon energies. Such intricate dependences can be explained by theoretical analyses employing first-principles calculations and group theory. Furthermore, these studies are a crucial step toward the applications of GaTe especially in optoelectronics and thermoelectrics, and provide a general methodology for the study of the anisotropy of light-matter interactions in 2D layered materials with in-plane anisotropy.
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Black phosphorus (BP) is a highly anisotropic allotrope of phosphorus with high promise for fast functional electronics and optoelectronics. We demonstrate that high-resolution and controlled structural modification of few-layer BP along arbitrary crystal direction can be achieved with nanometer-scale precision on a few-minute timescales leading to the formation of sub-nm wide armchair and zigzag BP nanoribbons. The nanoribbons are assembled, along with nanopores and nanogaps, using a combination of mechanical-liquid exfoliation and in situ transmission electron microscope (TEM) and scanning TEM nanosculpting. Here we report time-dependent structural properties of the one-dimensional systems under electron irradiation and probe their oxidation properties with electron energy-loss spectroscopy (EELS). Finally, we demonstrate the use of STEM to controllably narrow and thin the nanoribbons until they break into nanogaps. The observations are rationalized using density functional theory for transition state calculations and electronic band-structure evolution for the various stages of the narrowing procedure. In particular, we predict that the sub- and few-nm wide BP nanoribbons realized experimentally possess clear one-dimensional quantum confinement, even when the systems are made up of a few layers. We find the demonstration of this procedure is key for the development of BP-based electronic, optoelectronic, thermoelectric, and other applications in reduced dimensions.
A variety of van der Waals homo- and hetero- structures assembled by stamping monolayers together present optoelectronic properties suitable for diverse applications. Understanding the details of the interlayer stacking and resulting coupling is crucial for tuning these properties. Twisted bilayer transition metal dichalcogenides offer a great platform for developing a precise understanding of the structure/property relationship. Here, we study the low-frequency interlayer shear and breathing Raman modes (<50 cm-1) in twisted bilayer MoS 2 by Raman spectroscopy and first-principles modeling. Twisting introduces both rotational and translational shifts and significantly alters the interlayer stacking and coupling, leading to notable frequency and intensity changes of low-frequency modes. The frequency variation can be up to 8 cm-1 and the intensity can vary by a factor of ~5 for twisting near 0 and 60 , where the stacking is a mixture of multiple high-symmetry stacking patterns and is thus especially sensitive to twisting. Moreover, for twisting angles between 20 and 40 , the interlayer coupling is nearly constant since the stacking results in mismatched lattices over the entire sample. It follows that the Raman signature is relatively uniform. Interestingly, unlike the breathing mode, the shear mode is extremely sensitive to twisting: it disappears between 20 and 40 as its frequency drops to almost zero due to the stacking-induced mismatch. Note that for some samples, multiple breathing mode peaks appear, indicating non-uniform coupling across the interface. In contrast to the low-frequency interlayer modes, high-frequency intralayer Raman modes are much less sensitive to interlayer stacking and coupling, showing negligible changes upon twisting. Our research demonstrates the effectiveness of low-frequency Raman modes for probing the interfacial coupling and environment of twisted bilayer MoS2, and potentially other two-dimensional materials and heterostructures.
Significance It has been well known that the phonon drag effect—an extra electrical current induced by phonon heat flow via electron–phonon interaction—can lead to unusually high Seebeck coefficient at low temperatures. However, its use for improving thermoelectric performance has been controversial. Here, using first principles calculations we examine the phonon drag with detailed mode-specific contributions and reveal that even in heavily doped silicon at room temperature, phonon drag can still be significant, which challenges the previous belief that phonon drag vanishes in heavily doped samples. A phonon filter is designed to spectrally decouple the phonon drag from the heat conduction. Our simulation explores the coupled electron phonon transport and uncovers the possibility of optimizing the phonon drag for better thermoelectrics.
The monolayer of black phosphorus, or “phosphorene,” has recently emerged as a two-dimensional semiconductor with intriguing highly anisotropic transport properties. Existing calculations of its intrinsic phonon-limited electronic transport properties so far rely on the deformation potential approximation, which is in general not directly applicable to anisotropic materials since the deformation along one specific direction can scatter electrons traveling in all directions. We perform a first-principles calculation of the electron-phonon interaction in phosphorene based on density functional perturbation theory and Wannier interpolation. Our calculation reveals that (1) the high anisotropy provides extra phase space for electron-phonon scattering, and (2) optical phonons have appreciable contributions. Both effects cannot be captured by the deformation potential calculations. Furthermore, our simulation predicts carrier mobilities ~170 cm 2 /Vs for both electrons and holes at 300 K, and a thermoelectric figure of merit $zT$ of up to 0.14 in $p$-type impurity-free phosphorene at 500 K.
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As a new two-dimensional layered material, black phosphorus (BP) is a very promising material for nanoelectronics and nano-optoelectronics. We use Raman spectroscopy and first-principles theory to characterize and understand low-frequency (LF) interlayer breathing modes (<100 cm-1) in few-layer BP for the first time. Using 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 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 the breathing modes have a harmonic behavior, in contrast to HF Raman modes which exhibit anharmonicity.
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. Finally, 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.