Yanyuan Zhao

Interlayer Breathing and Shear Modes in Few-Trilayer MoS2 and WSe2

Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have recently attracted tremendous interest as potential valleytronic and nanoelectronic materials, in addition to being well-known as excellent lubricants in the bulk. The interlayer van der Waals (vdW) coupling and low-frequency phonon modes and how they evolve with the number of layers are important for both the mechanical and the electrical properties of 2D TMDs. Here we uncover the ultralow frequency interlayer breathing and shear modes in few-layer MoS2 and WSe2, prototypical layered TMDs, using both Raman spectroscopy and first principles calculations. Remarkably, the frequencies of these modes can be perfectly described using a simple linear chain model with only nearest-neighbor interactions. We show that the derived in-plane (shear) and out-of-plane (breathing) force constants from experiment remain the same from two-layer 2D crystals to the bulk materials, suggesting that the nanoscale interlayer frictional characteristics of these excellent lubricants should be independent of the number of layers.

Raman Spectroscopy of Few-Quintuple Layer Topological Insulator Bi2Se3 Nanoplatelets

We report on Raman spectroscopy of few quintuple layer topological insulator bismuth selenide (Bi2Se3) nanoplatelets (NPs), synthesized by a polyol method. The as-grown NPs exhibit excellent crystalline quality, hexagonal or truncated trigonal morphology, and uniformly flat surfaces down to a few quintuple layers. Both Stokes and anti-Stokes Raman spectroscopy for the first time resolve all four optical phonon modes from individual NPs down to 4 nm, where the out-of-plane vibrational A(1g)(1) mode shows a few wavenumbers red shift as the thickness decreases below ~15 nm. This thickness-dependent red shift is tentatively explained by a phonon softening due to the decreasing of the effective restoring force arising from a decrease of the van der Waals forces between adjacent layers. Quantitatively, we found that the 2D phonon confinement model proposed by Faucet and Campbell cannot explain the red shift values and the line shape of the A(1g)(1) mode, which can be described better by a Breit–Wigner–Fano resonance line shape. Considerable broadening (~17 cm(–1) for six quintuple layers) especially for the in-plane vibrational mode E(g)(2) is identified, suggesting that the layer-to-layer stacking affects the intralayer bonding. Therefore, a significant reduction in the phonon lifetime of the in-plane vibrational modes is probably due to an enhanced electron–phonon coupling in the few quintuple layer regime.

Large-Area Synthesis of Monolayer and Few-Layer MoSe2 Films on SiO2 Substrates

We present successful synthesis of large area atomically thin MoSe2 films by selenization of MoO3 in a vapor transport chemical vapor deposition (CVD) system. The homogeneous thin film can reach an area of 1 × 1 cm(2) consisting primarily of monolayer and bilayer MoSe2 film. Scanning transmission electron microscopy (STEM) images reveal the highly crystalline nature of the thin film and the atomic structure of grain boundaries in monolayers. Raman and photoluminescence spectroscopy confirm the high quality of as-grown MoSe2 in optics, and electronic transport measurements highlight the potential applications of the sample in nanoelectronics.

Dynamics of bound exciton complexes in CdS nanobelts.

Intrinsic defects such as vacancies, interstitials, and anti-sites often introduce rich luminescent properties in II-VI semiconductor nanomaterials. A clear understanding of the dynamics of the defect-related excitons is particularly important for the design and optimization of nanoscale optoelectronic devices. In this paper, low-temperature steady-state and time-resolved photoluminescence (PL) spectroscopies have been carried out to investigate the emission of cadmium sulfide (CdS) nanobelts that originates from the radiative recombination of excitons bound to neutral donors (I(2)) and the spatially localized donor-acceptor pairs (DAP), in which the assignment is supported by first principle calculations. Our results verify that the shallow donors in CdS are contributed by sulfur vacancies while the acceptors are contributed by cadmium vacancies. At high excitation intensities, the DAP emission saturates and the PL is dominated by I(2) emission. Beyond a threshold power of approximately 5 μW, amplified spontaneous emission (ASE) of I(2) occurs. Further analysis shows that these intrinsic defects created long-lived (spin triplet) DAP trap states due to spin-polarized Cd vacancies which become saturated at intense carrier excitations.

Interface Driven Energy Filtering of Thermoelectric Power in Spark Plasma Sintered Bi2Te2.7Se0.3 Nanoplatelet Composites

Control of competing parameters such as thermoelectric (TE) power and electrical and thermal conductivities is essential for the high performance of thermoelectric materials. Bulk-nanocomposite materials have shown a promising improvement in the TE performance due to poor thermal conductivity and charge carrier filtering by interfaces and grain boundaries. Consequently, it has become pressingly important to understand the formation mechanisms, stability of interfaces and grain boundaries along with subsequent effects on the physical properties. We report here the effects of the thermodynamic environment during spark plasma sintering (SPS) on the TE performance of bulk-nanocomposites of chemically synthesized Bi(2)Te(2.7)Se(0.3) nanoplatelets. Four pellets of nanoplatelets powder synthesized in the same batch have been made by SPS at different temperatures of 230, 250, 280, and 350 °C. The X-ray diffraction, transmission electron microscopy, thermoelectric, and thermal transport measurements illustrate that the pellet sintered at 250 °C shows a minimum grain growth and an optimal number of interfaces for efficient TE figure of merit, ZT∼0.55. For the high temperature (350 °C) pelletized nanoplatelet composites, the concurrent rise in electrical and thermal conductivities with a deleterious decrease in thermoelectric power have been observed, which results because of the grain growth and rearrangements of the interfaces and grain boundaries. Cross section electron microscopy investigations indeed show significant grain growth. Our study highlights an optimized temperature range for the pelletization of the nanoplatelet composites for TE applications. The results provide a subtle understanding of the grain growth mechanism and the filtering of low energy electrons and phonons with thermoelectric interfaces.

Anomalous frequency trends in MoS2 thin films attributed to surface effects

2g mode with decreasing thickness, a trend that is not understood. Here, we combine experimental Raman scattering and theoretical studies to clarify and explain this trend. Special attention is given to understanding the surface effect on Raman frequencies by using a force constants model based on first-principles calculations. Surface effects refer to the larger Mo-S force constants at the surface of thin film MoS2, which results from a loss of neighbours in adjacent MoS2 layers. Withoutsurfaceeffects,thefrequenciesofbothout-of-plane A1g andin-plane E 1g modesdecreasewithdecreasing thickness. However, the E 1g mode blue shifts while the A1g mode red shifts once the surface effect is included, in agreement with the experiment. Our results show that competition between the thickness effect and the surface effect determines the mechanical properties of two-dimensional MoS2, which we believe applies to other layered materials.

Rapid and Nondestructive Identification of Polytypism and Stacking Sequences in Few‐Layer Molybdenum Diselenide by Raman Spectroscopy

Various combinations of interlayer shear modes emerge in few-layer molybdenum diselenide grown by chemical vapor deposition depending on the stacking configuration of the sample. Raman measurements may also reveal polytypism and stacking faults, as supported by first principles calculations and high-resolution transmission electron microscopy. Thus, Raman spectroscopy is an important tool in probing stacking-dependent properties in few-layer 2D materials.

Interfacial Interactions in van der Waals Heterostructures of MoS2 and Graphene

Interfacial coupling between neighboring layers of van der Waals heterostructures (vdWHs), formed by vertically stacking more than two types of two-dimensional materials (2DMs), greatly affects their physical properties and device performance. Although high-resolution cross-sectional scanning tunneling electron microscopy can directly image the atomically sharp interfaces in the vdWHs, the interfacial coupling and lattice dynamics of vdWHs formed by two different types of 2DMs, such as semimetal and semiconductor, are not clear so far. Here, we report the ultralow-frequency Raman spectroscopy investigation on interfacial couplings in the vdWHs formed by graphene and MoS2 flakes. Because of the significant interfacial layer-breathing couplings between MoS2 and graphene flakes, a series of layer-breathing modes with frequencies dependent on their layer numbers are observed in the vdWHs, which can be described by the linear chain model. It is found that the interfacial layer-breathing force constant between MoS2 and graphene, α0⊥(I) = 60 × 1018 N/m3, is comparable with the layer-breathing force constant of multilayer MoS2 and graphene. The results suggest that the interfacial layer-breathing couplings in the vdWHs formed by MoS2 and graphene flakes are not sensitive to their stacking order and twist angle between the two constituents. Our results demonstrate that the interfacial interlayer coupling in vdWHs formed by two-dimensional semimetals and semiconductors can lead to new lattice vibration modes, which not only can be used to measure the interfacial interactions in vdWHs but also is beneficial to fundamentally understand the properties of vdWHs for further engineering the vdWHs-based electronic and photonic devices.

Controlled synthesis of CdE (E = S, Se and Te) nanowires

This work focused on a catalyst-free solution-based method to synthesize single-crystal CdE (E = S, Se and Te) nanowires. Using the hot coordinating solvents method, we have successfully synthesized high aspect ratio CdE nanowires. In this paper, we present our very recent results on the synthesis of CdTe nanowires and summarize our understanding of the effect of reaction parameters on the growth of CdE nanowires. The reaction parameters include ligands for Cd-complexes and E-complexes, ligand-to-Cd mole ratio, Cd-to-E mole ratio, precursor concentration, reaction temperature and the injection process. We propose the optimum conditions for the growth of CdE nanocrystals with a large aspect ratio. Possible growth mechanisms were also investigated using time-dependent studies. Furthermore, a Raman study shows a higher concentration of tellurium on the surface of CdTe nanowires. This is understandable because the free energy of Te is smaller than that of CdTe and thus Te crystals can easily form during the synthesis. Our high aspect-ratio nanowires have good dispersibility and exhibit huge potential applications in areas such as solution processed photovoltaic cells and transistors.

Te-seeded growth of few-quintuple layer Bi2Te3 nanoplates

We report on a Te-seeded epitaxial growth of ultrathin Bi2Te3 nanoplates (down to three quintuple layers (QL)) with large planar sizes (up to tens of micrometers) through vapor transport. Optical contrast has been systematically investigated for the as-grown Bi2Te3 nanoplates on the SiO2/Si substrates, experimentally and computationally. The high and distinct optical contrast provides a fast and convenient method for the thickness determination of few-QL Bi2Te3 nanoplates. By aberration-corrected scanning transmission electron microscopy, a hexagonal crystalline structure has been identified for the Te seeds, which form naturally during the growth process and initiate an epitaxial growth of the rhombohedralstructured Bi2Te3 nanoplates. The epitaxial relationship between Te and Bi2Te3 is identified to be perfect along both in-plane and out-of-plane directions of the layered nanoplate. Similar growth mechanism might be expected for other bismuth chalcogenide layered materials.