Unveiling the MIL-53(Al) MOF: Tuning Photoluminescence and Structural Properties via Volatile Organic Compounds Interactions.

MIL-53(Al) is a metal-organic framework (MOF) with unique properties, including structural flexibility, thermal stability, and luminescence. Its ability to adsorb volatile organic compounds (VOCs) and water vapor makes it a promising platform for sensing applications. This study investigated the adsorption mechanism of MIL-53(Al) with different VOCs, including ketones, alcohols, aromatics, and water molecules, focusing on structural transformations due to pore size variation and photoluminescence properties. The reported results assess MIL-53(Al) selectivity towards different VOCs and provide insights into their fundamental properties and potential applications in sensing.

Defects in epitaxial 4H-SiC revealed by exciton recombination.

In this work, we conducted an analysis of 4H-SiC epitaxial layer grown on two distinct 4H-SiC substrates (both 6 inches in diameter) using non-invasive techniques such as micro-Raman spectroscopy, steady-state absorption spectroscopy and time-resolved photoluminescence spectroscopy. We have shown that despite the doping homogeneity, confirmed by micro-Raman and steady-state absorption spectroscopy, the carrier lifetime, assessed by monitoring the excitonic band at 3.2 eV by time-resolved photoluminescence spectroscopy, depends on the position on the wafer. This variability is attributed to the presence of defects, such as impurities or point defects, which are not uniformly distributed on the epitaxial layer and that, in addition to extended defects, affect the charge carrier recombination. Additionally, it is found that interactions with the underlying substrate could contribute to these effects as evidenced in regions of the substrate characterized by differences of doping.

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization.

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS2 obtained by sulfurization at 800 °C of very thin MoO3 films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO2/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS2, with only a small percentage of residual MoO3 present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2-3 layers) of MoS2 nearly aligned with the SiO2 surface in the case of the thinnest (~2.8 nm) MoO3 film, whereas multilayers of MoS2 partially standing up with respect to the substrate were observed for the ~4.2 nm one. Such different configurations indicate the prevalence of different mechanisms (i.e., vapour-solid surface reaction or S diffusion within the film) as a function of the thickness. The uniform thickness distribution of the few-layer and multilayer MoS2 was confirmed by Raman mapping. Furthermore, the correlative plot of the characteristic A1g-E2g Raman modes revealed a compressive strain (ε ≈ -0.78 ± 0.18%) and the coexistence of n- and p-type doped areas in the few-layer MoS2 on SiO2, where the p-type doping is probably due to the presence of residual MoO3. Nanoscale resolution current mapping by C-AFM showed local inhomogeneities in the conductivity of the few-layer MoS2, which are well correlated to the lateral changes in the strain detected by Raman. Finally, characteristic spectroscopic signatures of the defects/disorder in MoS2 films produced by sulfurization were identified by a comparative analysis of Raman and photoluminescence (PL) spectra with CVD grown MoS2 flakes.

Ultrafast Interface Charge Separation in Carbon Nanodot-Nanotube Hybrids.

Carbon dots are an emerging family of zero-dimensional nanocarbons behaving as tunable light harvesters and photoactivated charge donors. Coupling them to carbon nanotubes, which are well-known electron acceptors with excellent charge transport capabilities, is very promising for several applications. Here, we first devised a route to achieve the stable electrostatic binding of carbon dots to multi- or single-walled carbon nanotubes, as confirmed by several experimental observations. The photoluminescence of carbon dots is strongly quenched when they contact either semiconductive or conductive nanotubes, indicating a strong electronic coupling to both. Theoretical simulations predict a favorable energy level alignment within these complexes, suggesting a photoinduced electron transfer from dots to nanotubes, which is a process of high functional interest. Femtosecond transient absorption confirms indeed an ultrafast (<100 fs) electron transfer independent of nanotubes being conductive or semiconductive in nature, followed by a much slower back electron transfer (≈60 ps) from the nanotube to the carbon dots. The high degree of charge separation and delocalization achieved in these nanohybrids entails significant photocatalytic properties, as we demonstrate by the reduction of silver ions in solution. The results are very promising in view of using these "all-carbon" nanohybrids as efficient light harvesters for applications in artificial photocatalysis and photosynthesis.

A Comparative Study of Top-Down and Bottom-Up Carbon Nanodots and Their Interaction with Mercury Ions.

We report a study of carbon dots produced via bottom-up and top-down routes, carried out through a multi-technique approach based on steady-state fluorescence and absorption, time-resolved fluorescence spectroscopy, Raman spectroscopy, infrared spectroscopy, and atomic force microscopy. Our study focuses on a side-to-side comparison of the fundamental structural and optical properties of the two families of fluorescent nanoparticles, and on their interaction pathways with mercury ions, which we use as a probe of surface emissive chromophores. Comparison between the two families of carbon dots, and between carbon dots subjected to different functionalization procedures, readily identifies a few key structural and optical properties apparently common to all types of carbon dots, but also highlights some critical differences in the optical response and in the microscopic mechanism responsible of the fluorescence. The results also provide suggestions on the most likely interaction sites of mercury ions at the surface of carbon dots and reveal details on mercury-induced fluorescence quenching that can be practically exploited to optimize sensing applications of carbon dots.

Strain, Doping, and Electronic Transport of Large Area Monolayer MoS2 Exfoliated on Gold and Transferred to an Insulating Substrate.

Gold-assisted mechanical exfoliation currently represents a promising method to separate ultralarge (centimeter scale) transition metal dichalcogenide (TMD) monolayers (1L) with excellent electronic and optical properties from the parent van der Waals (vdW) crystals. The strong interaction between Au and chalcogen atoms is key to achieving this nearly perfect 1L exfoliation yield. On the other hand, it may significantly affect the doping and strain of 1L TMDs in contact with Au. In this paper, we systematically investigated the morphology, strain, doping, and electrical properties of large area 1L MoS2 exfoliated on ultraflat Au films (0.16-0.21 nm roughness) and finally transferred to an insulating Al2O3 substrate. Raman mapping and correlative analysis of the E' and A1' peak positions revealed a moderate tensile strain (ε ≈ 0.2%) and p-type doping (n ≈ -0.25 × 1013 cm-2) of 1L MoS2 in contact with Au. Nanoscale resolution current mapping and current-voltage (I-V) measurements by conductive atomic force microscopy (C-AFM) showed direct tunneling across the 1L MoS2 on Au, with a broad distribution of tunneling barrier values (ΦB from 0.7 to 1.7 eV) consistent with p-type doping of MoS2. After the final transfer of 1L MoS2 on Al2O3/Si, the strain was converted to compressive strain (ε ≈ -0.25%). Furthermore, an n-type doping (n ≈ 0.5 × 1013 cm-2) was deduced by Raman mapping and confirmed by electrical measurements of an Al2O3/Si back-gated 1L MoS2 transistor. These results provide a deeper understanding of the Au-assisted exfoliation mechanism and can contribute to its widespread application for the realization of novel devices and artificial vdW heterostructures.

Dynamic Modification of Fermi Energy in Single-Layer Graphene by Photoinduced Electron Transfer from Carbon Dots.

Graphene (Gr)-a single layer of two-dimensional sp2 carbon atoms-and Carbon Dots (CDs)-a novel class of carbon nanoparticles-are two outstanding nanomaterials, renowned for their peculiar properties: Gr for its excellent charge-transport, and CDs for their impressive emission properties. Such features, coupled with a strong sensitivity to the environment, originate the interest in bringing together these two nanomaterials in order to combine their complementary properties. In this work, the investigation of a solid-phase composite of CDs deposited on Gr is reported. The CD emission efficiency is reduced by the contact of Gr. At the same time, the Raman analysis of Gr demonstrates the increase of Fermi energy when it is in contact with CDs under certain conditions. The interaction between CDs and Gr is modeled in terms of an electron-transfer from photoexcited CDs to Gr, wherein an electron is first transferred from the carbon core to the surface states of CDs, and from there to Gr. There, the accumulated electrons determine a dynamical n-doping effect modulated by photoexcitation. The CD-graphene interaction unveiled herein is a step forward in the understanding of the mutual influence between carbon-based nanomaterials, with potential prospects in light conversion applications.

In-situ monitoring by Raman spectroscopy of the thermal doping of graphene and MoS2 in O2-controlled atmosphere.

The effects of temperature and atmosphere (air and O2) on the doping of monolayers of graphene (Gr) on SiO2 and Si substrates, and on the doping of MoS2 multilayer flakes transferred on the same substrates have been investigated. The investigations were carried out by in situ micro-Raman spectroscopy during thermal treatments up to 430 °C, and by atomic force microscopy (AFM). The spectral positions of the G and 2D Raman bands of Gr undergo only minor changes during treatment, while their amplitude and full width at half maximum (FWHM) vary as a function of the temperature and the used atmosphere. The thermal treatments in oxygen atmosphere show, in addition to a thermal effect, an effect attributable to a p-type doping through oxygen. The thermal broadening of the line shape, found during thermal treatments by in situ Raman measurements, can be related to thermal phonon effects. The absence of a band shift results from the balance between a red shift due to thermal effects and a blue shift induced by doping. This shows the potential of in situ measurements to follow the doping kinetics. The treatment of MoS2 in O2 has evidenced a progressive erosion of the flakes without relevant spectral changes in their central zone during in situ measurements. The formation of MoO3 on the edges of the flakes is observed indicative of the oxygen-activated transformation.

Luminescence mechanisms of defective ZnO nanoparticles.

ZnO nanoparticles (NPs) synthesized by pulsed laser ablation (PLAL) of a zinc plate in deionized water were investigated by time-resolved photoluminescence (PL) and complementary techniques (TEM, AFM, µRaman). HRTEM images show that PLAL produces crystalline ZnO NPs in wurtzite structure with a slightly distorted lattice parameter a. Consistently, optical spectra show the typical absorption edge of wurtzite ZnO (Eg = 3.38 eV) and the related excitonic PL peaked at 3.32 eV with a subnanosecond lifetime. ZnO NPs display a further PL peaking at 2.2 eV related to defects, which shows a power law decay kinetics. Thermal annealing in O2 and in a He atmosphere produces a reduction of the A1(LO) Raman mode at 565 cm(-1) associated with oxygen vacancies, accompanied by a decrease of defect-related emission at 2.2 eV. Based on our experimental results the emission at 2.2 eV is proposed to originate from a photo-generated hole in the valence band recombining with an electron deeply trapped in a singly ionized oxygen vacancy. This investigation clarifies important aspects of the photophysics of ZnO NPs and indicates that ZnO emission can be controlled by thermal annealing, which is important in view of optoelectronic applications.

Morphological and Chemical Evolution of Gradually Deposited Diamond-Like Carbon Films on Polyethylene Terephthalate: From Subplantation Processes to Structural Reorganization by Intrinsic Stress Release Phenomena.

Diamond-like carbon (DLC) films on polyethylene terephthalate (PET) are nowadays intensively studied composites due to their excellent gas barrier properties and biocompatibility. Despite their applicative features being highly explored, the interface properties and structural film evolution of DLC coatings on PET during deposition processes are still sparsely investigated. In this study two different types of DLC films were gradually deposited on PET by radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) using acetylene plasma. The surface morphology of the deposited samples has been analyzed by atomic force microscopy (AFM). Their chemical composition was investigated by diffusive reflectance infrared Fourier transform (DRIFT) and Raman spectroscopy analysis and the surface wettability by contact angle measurements. Subplantation processes and interface effects are revealed through the morphological and chemical analysis of both types. During plasma deposition processes the increasing carbon load causes the rise of intrinsic film stress. It is proven that stress release phenomena cause the transition between polymer-like to a more cross-linked DLC network by folding dehydrogenated chains into closed 6-fold rings. These findings significantly lead to an enhanced understanding in DLC film growth mechanism by RF-PECVD processes.

Visible-ultraviolet vibronic emission of silica nanoparticles.

We report the study of the visible-ultraviolet emission properties and the structural features of silica nanoparticles prepared through a laboratory sol-gel technique. Atomic force microscopy, Raman and Infrared investigations highlighted the 10 nm size, purity and porosity of the obtained nanoparticles. By using time resolved photoluminescence techniques in air and in a vacuum we were able to single out two contributions in the visible emission: the first, stable in both atmospheres, is a typical fast blue band centered around 2.8 eV; the second, only observed in a vacuum around the 3.0-3.5 eV range, is a vibrational progression with two phonon modes at 1370 cm(-1) and 360 cm(-1). By fully characterizing the spectroscopic features of this structured emission, we determine its vibronic properties and clarify the different origins with respect to the blue luminescent defect.