Thickness-Dependent Phonon Renormalization and Enhanced Raman Scattering in Ultrathin Silicon Nanomembranes

We report on the thickness-dependent Raman spectroscopy of ultrathin silicon (Si) nanomembranes (NMs), whose thicknesses range from 2 to 18 nm, using several excitation energies. We observe that the Raman intensity depends on the thickness and the excitation energy due to the combined effects of interference and resonance from the band-structure modulation. Furthermore, confined acoustic phonon modes in the ultrathin Si NMs were observed in ultralow-frequency Raman spectra, and strong thickness dependence was observed near the quantum limit, which was explained by calculations based on a photoelastic model. Our results provide a reliable method with which to accurately determine the thickness of Si NMs with thicknesses of less than a few nanometers

Multiple Coordination Exchanges for Room-Temperature Activation of Open-Metal Sites in Metal–Organic Frameworks

The activation of open coordination sites (OCSs) in metal–organic frameworks (MOFs), i.e., the removal of solvent molecules coordinated at the OCSs, is an essential step that is required prior to the use of MOFs in potential applications such as gas chemisorption, separation, and catalysis because OCSs often serve as key sites in these applications. Recently, we developed a “chemical activation” method involving dichloromethane (DCM) treatment at room temperature, which is considered to be a promising alternative to conventional thermal activation (TA), because it does not require the application of external thermal energy, thereby preserving the structural integrity of the MOFs. However, strongly coordinating solvents such as <i>N</i>,<i>N</i>-di­methyl­form­amide (DMF), <i>N</i>,<i>N</i>-di­ethyl­form­amide (DEF), and dimethyl sulfoxide (DMSO) are difficult to remove solely with the DCM treatment. In this report, we demonstrate a multiple coordination exchange (CE) process executed initially with acetonitrile (MeCN), methanol (MeOH), or ethanol (EtOH) and subsequently with DCM to achieve the complete activation of OCSs that possess strong extracoordination. Thus, this process can serve as an effective “chemical route” to activation at room temperature that does not require applying heat. To the best of our knowledge, no previous study has demonstrated the activation of OCSs using this multiple CE process, although MeOH and/or DCM has been popularly used in pretreatment steps prior to the TA process. Using MOF-74­(Ni), we demonstrate that this multiple CE process can safely activate a thermally unstable MOF without inflicting structural damage. Furthermore, on the basis of in situ ¹H nuclear magnetic resonance (¹H NMR) and Raman studies, we propose a plausible mechanism for the activation behavior of multiple CE

A Chemical Route to Activation of Open Metal Sites in the Copper-Based Metal–Organic Framework Materials HKUST‑1 and Cu-MOF‑2

Open coordination sites (OCSs) in metal–organic frameworks (MOFs) often function as key factors in the potential applications of MOFs, such as gas separation, gas sorption, and catalysis. For these applications, the activation process to remove the solvent molecules coordinated at the OCSs is an essential step that must be performed prior to use of the MOFs. To date, the thermal method performed by applying heat and vacuum has been the only method for such activation. In this report, we demonstrate that methylene chloride (MC) itself can perform the activation role: this process can serve as an alternative “chemical route” for the activation that does not require applying heat. To the best of our knowledge, no previous study has demonstrated this function of MC, although MC has been popularly used in the pretreatment step prior to the thermal activation process. On the basis of a Raman study, we propose a plausible mechanism for the chemical activation, in which the function of MC is possibly due to its coordination with the Cu²⁺ center and subsequent spontaneous decoordination. Using HKUST-1 film, we further demonstrate that this chemical activation route is highly suitable for activating large-area MOF films

Local Strain Induced Band Gap Modulation and Photoluminescence Enhancement of Multilayer Transition Metal Dichalcogenides

The photocarrier relaxation between direct and indirect band gaps along the high symmetry K−Γ line in the Brillion zone reveals interesting electronic properties of the transition metal dichalcogenides (TMDs) multilayer films. In this study, we reported on the local strain engineering and tuning of an electronic band structure of TMDs multilayer films along the K−Γ line by artificially creating one-dimensional wrinkle structures. Significant photoluminescence (PL) intensity enhancement in conjunction with continuously tuned optical energy gaps was recorded at the high strain regions. A direct optical band gap along K–K points and an indirect optical gap along Γ–K points measured from the PL spectra of multilayer samples monotonically decreased as the strain increased, while the indirect band gap along Λ–Γ was unaffected owing to the same level of local strain in the range of 0%–2%. The experimental results of band gap tuning were in agreement with the density functional theory calculation results. Local strain modified the band structure in which K-conduction band valley (CBV) was aligned below the Λ-CBV, and this explained the observed local PL enhancement that made the material indirect via the K−Γ transition. The study also reported experimental evidence for the funneling of photogenerated excitons toward regions of a higher strain at the top of the wrinkle geometry

Nonconventional Strain Engineering for Uniform Biaxial Tensile Strain in MoS₂ Thin Film Transistors

Strain engineering has been employed as a crucial technique to enhance the electrical properties of semiconductors, especially in Si transistor technologies. Recent theoretical investigations have suggested that strain engineering can also markedly enhance the carrier mobility of two-dimensional (2D) transition-metal dichalcogenides (TMDs). The conventional methods used in strain engineering for Si and other bulk semiconductors are difficult to adapt to ultrathin 2D TMDs. Here, we report a strain engineering approach to apply the biaxial tensile strain to MoS2. Metal-organic chemical vapour deposition (MOCVD)-grown large-area MoS2 films were transferred onto SiO2/Si substrate, followed by the selective removal of the underneath Si. The release of compressive residual stress in the oxide layer induces strain in MoS2 on top of the SiO2 layer. The amount of strain can be precisely controlled by the thickness of oxide stressors. After the transistors were fabricated with strained MoS2 films, the array of strained transistors was transferred onto plastic substrates. This process ensured that the MoS2 channels maintained a consistent tensile strain value across a large area