Cubic (space group: Fmm) iridium phosphide, Ir2P, has been synthesized at high pressure and high temperature. Angle-dispersive synchrotron X-ray diffraction measurements on Ir2P powder using a diamond-anvil cell at room temperature and high pressures (up to 40.6 GPa) yielded a bulk modulus of B[subscript 0] = 306(6) GPa and its pressure derivative B0′ = 6.4(5). Such a high bulk modulus attributed to the short and strongly covalent Ir-P bonds as revealed by first – principles calculations and three-dimensionally distributed [IrP4] tetrahedron network. Indentation testing on a well–sintered polycrystalline sample yielded the hardness of 11.8(4) GPa. Relatively low shear modulus of ~64 GPa from theoretical calculations suggests a complicated overall bonding in Ir2P with metallic, ionic, and covalent characteristics. In addition, a spin glass behavior is indicated by magnetic susceptibility measurements.
Transition metal trichalcogenides form a class of layered materials with strong in-plane anisotropy. For example, titanium trisulfide (TiS3) whiskers are made out of weakly interacting TiS3 layers, where each layer is made of weakly interacting quasi-one-dimensional chains extending along the b axis. Here we establish the unusual vibrational properties of TiS3 both experimentally and theoretically. Unlike other two-dimensional systems, the Raman active peaks of TiS3 have only out-of-plane vibrational modes, and interestingly some of these vibrations involve unique rigid-chain vibrations and S–S molecular oscillations. High-pressure Raman studies further reveal that the AgS-S S-S molecular mode has an unconventional negative pressure dependence, whereas other peaks stiffen as anticipated. Various vibrational modes are doubly degenerate at ambient pressure, but the degeneracy is lifted at high pressures. These results establish the unusual vibrational properties of TiS3 with strong in-plane anisotropy, and may have relevance to understanding of vibrational properties in other anisotropic two-dimensional material systems.
We present two-dimensional Mg(OH)2 sheets and their vertical heterojunctions with CVD-MoS2 for the first time as flexible 2D insulators with anomalous lattice vibration and chemical and physical properties. New hydrothermal crystal growth technique enabled isolation of environmentally stable monolayer Mg(OH)2 sheets. Raman spectroscopy and vibrational calculations reveal that the lattice vibrations of Mg(OH)2 have fundamentally different signature peaks and dimensionality effects compared to other 2D material systems known to date. Sub-wavelength electron energy-loss spectroscopy measurements and theoretical calculations show that Mg(OH)2 is a 6 eV direct-gap insulator in 2D, and its optical band gap displays strong band renormalization effects from monolayer to bulk, marking the first experimental confirmation of confinement effects in 2D insulators. Interestingly, 2D-Mg(OH)2 sheets possess rather strong surface polarization (charge) effects which is in contrast to electrically neutral h-BN materials. Using 2D-Mg(OH)2 sheets together with CVD-MoS2 in the vertical stacking shows that a strong change transfer occurs from n-doped CVD-MoS2 sheets to Mg(OH)2, naturally depleting the semiconductor, pushing towards intrinsic doping limit and enhancing overall optical performance of 2D semiconductors. Results not only establish unusual confinement effects in 2D-Mg(OH)2, but also offer novel 2D-insulating material with unique physical, vibrational, and chemical properties for potential applications in flexible optoelectronics.
Binary transition metal dichalcogenide monolayers share common properties such as a direct optical bandgap, spin-orbit splittings of hundreds of meV, light–matter interaction dominated by robust excitons and coupled spin-valley states. Here we demonstrate spin-orbit-engineering in Mo[(1-x)]WxSe2 alloy monolayers for optoelectronics and applications based on spin- and valley-control. We probe the impact of the tuning of the conduction band spin-orbit spin-splitting on the bright versus dark exciton population. For MoSe2 monolayers, the photoluminescence intensity decreases as a function of temperature by an order of magnitude (4–300 K), whereas for WSe2 we measure surprisingly an order of magnitude increase. The ternary material shows a trend between these two extreme behaviors. We also show a non-linear increase of the valley polarization as a function of tungsten concentration, where 40% tungsten incorporation is sufficient to achieve valley polarization as high as in binary WSe2.
In this letter, we study the near-field radiative heat transfer between two metamaterial substrates coated with silicon carbide (SiC) thin films. It is known that metamaterials can enhance the near-field heat transfer over ordinary materials due to excitation of magnetic plasmons associated with s polarization, while strong surface phonon polariton exists for SiC. By careful tuning of the optical properties of metamaterial, it is possible to excite electrical and magnetic resonances for the metamaterial and surface phonon polaritons for SiC at different spectral regions, resulting in the enhanced heat transfer. The effect of the SiC film thickness at different vacuum gaps is investigated. Results obtained from this study will be beneficial for application of thin film coatings for energy harvesting.
In this work, a selective solar absorber made of nanostructured titanium gratings deposited on an ultrathin MgF2 spacer and a tungsten ground film is proposed and experimentally demonstrated. Normal absorptance of the fabricated solar absorber is characterized to be higher than 0.9 in the UV, visible and, near infrared (IR) regime, while the mid-IR emittance is around 0.2. The high broadband absorption in the solar spectrum is realized by the excitation of surface plasmon and magnetic polariton resonances, while the low mid-IR emittance is due to the highly reflective nature of the metallic components. Further directional and polarized reflectance measurements show wide-angle and polarization-insensitive high absorption within solar spectrum. Temperature-dependent spectroscopic characterization indicates that the optical properties barely change at elevated temperatures up to 350 °C. The solar-to-heat conversion efficiency with the fabricated metamaterial solar absorber is predicted to be 78% at 100 °C without optical concentration or 80% at 400 °C with 25 suns. The performance could be further improved with better fabrication processes and geometric optimization during metamaterial design. The strong spectral selectivity, favorable diffuse-like behavior, and good thermal stability make the metamaterial selective absorber promising for significantly enhancing solar thermal energy harvesting in various systems at mid to high temperatures.
materials for lithium-based batteries: silicon (Si) and metal lithium (Li). It will focus on
studying the mechanical behaviors of the two materials during charge and discharge and
understanding how these mechanical behaviors may affect their electrochemical
performance.
In the first part, amorphous Si anode will be studied. Despite many existing studies
on silicon (Si) anodes for lithium ion batteries (LIBs), many essential questions still exist
on compound formation, composition, and properties. Here it is shown that some
previously accepted findings do not truthfully reflect the actual lithiation mechanisms in
realistic battery configurations. Furthermore the correlation between structure and
mechanical properties in these materials has not been properly established. Here, a rigorous
and thorough study is performed to comprehensively understand the electrochemical
reaction mechanisms of amorphous-Si (a-Si) in a realistic LIB configuration. In-depth
microstructural characterization was performed and correlations were established between
Li-Si composition, volumetric expansion, and modulus/hardness. It is found that the
lithiation process of a-Si in a real battery setup is a single-phase reaction rather than the
accepted two-phase reaction obtained from in-situ TEM experiments. The findings in this
dissertation establish a reference to quantitatively explain many key metrics for lithiated a
Si as anodes in real LIBs, and can be used to rationally design a-Si based high-performance
LIBs guided by high-fidelity modeling and simulations.
In the second part, Li metal anode will be investigated. Problems related to dendrite
growth on lithium metal anodes such as capacity loss and short circuit present major
barriers to the next-generation high-energy-density batteries. The development of
successful mitigation strategies is impeded by the incomplete understanding of the Li
dendrite growth mechanisms. Here the enabling role of plating residual stress in dendrite
initiation through novel experiments of Li electrodeposition on soft substrates is confirmed,
and the observations is explained with a stress-driven dendrite growth model. Dendrite
growth is mitigated on such soft substrates through surface-wrinkling-induced stress
relaxation in deposited Li film. It is demonstrated that this new dendrite mitigation
mechanism can be utilized synergistically with other existing approaches in the form of
three-dimensional (3D) soft scaffolds for Li plating, which achieves superior coulombic
efficiency over conventional hard copper current collectors under large current density.
Alloying selenium into ReS2 in the creation of ReS2xSe2-x, tunes the band gap and changes its vibrational spectrum. Depositing this alloy using bottom up approach has resulted in the loss of crystallinity. This loss of crystallinity was evidenced by grain boundaries and point defect shown by TEM images.
Also, in the creation of TiS3xSe3-x, by alloying Se into TiS3, a fixed ratio of 8% selenium deposit into TiS3 host matrix is observed. This is despite the vastly differing precursor amounts and growth temperatures, as evinced by detailed TEM, EDAX, TEM diffraction, and Raman spectroscopy measurements. This unusual behavior contrasts with other well-known layered material systems such as MoSSe, WMoS2 where continuous alloying can be attained. Cluster expansion theory calculations suggest that only limited composition (x) can be achieved. Considering the fact that TiSe3 vdW crystals have not been synthesized in the past, these alloying rejections can be attributed to energetic instability in the ternary phase diagrams estimated by calculations performed. Overall findings highlight potential means and challenges in achieving stable alloying in promising direct gap and high carrier mobility TiS3 materials.
The pads were created using varying amounts of LM and matrix materials ranging from copper microspheres to diamond powder mixed into PDMS using a high-speed mixer. The material was then cast into molds and cured to create the pads. Once the pads were created, the difficulty came in quantifying their thermal properties. A stepped bar apparatus (SBA) following ASTM D5470 was created to measure the thermal resistance of the pads but it was determined that thermal conductivity was a more usable metric of the pads’ performance. This meant that the pad’s in-situ thickness was needed during testing, prompting the installation of a linear encoder to measure the thickness. The design and analysis of the necessary modification and proposed future design is further detailed in the following paper.
