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4H-SiC is one of the most promising indirect wide-bandgap (3.3 eV) semiconductor for power devices used in the emerging area of high-voltage and high-temperature electronics as well as space and radiation harsh environments applications. The wide diffusion of devices in SiC is related to the high quality of the crystals, both for substrates and epitaxial layers. In this work, we performed thermal treatments in Argon atmosphere at temperatures below 2000°C with the aim to study the thermal stability of substrates of 4H-SiC. The wafer substrates were characterized by micro-Raman spectroscopy, Atomic Force Microscopy and Electrostatic Force Microscopy. The thermal treatments induced inhomogeneity of the wafer surface due to a graphitization process starting from 1600°C.

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C60 and C70, with remarkably large binding constants (ca. 107 M−1), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These results demonstrate saddle-shaped PAHs with dibenzocycloheptatrienone motifs as structural components for new macrocycles displaying molecular receptor abilities and versatile photochemical responses with promising electron-donor properties in host-guest complexes., Junta de Andalucia-Consejeria de Universidad, Investigacion e Innovacion and FEDER(ERDF) "A way of making Europe" P18-FR-2877, ERDF "A way of making Europe", Universidad de Granada / CBUA

In this paper, 2D/3D heterojunction diodes have been fabricated by pulsed laser deposition (PLD) of MoS2 on 4H-SiC(0001) surfaces with different doping levels, i.e., n− epitaxial doping (≈1016 cm−3) and n+ ion implantation doping (>1019 cm−3). After assessing the excellent thickness uniformity (≈3L-MoS2) and conformal coverage of the PLD-grown films by Raman mapping and transmission electron microscopy, the current injection across the heterojunctions is investigated by temperature-dependent current–voltage characterization of the diodes and by nanoscale current mapping with conductive atomic force microscopy. A wide tunability of the transport properties is shown by the SiC surface doping, with highly rectifying behavior for the MoS2/n− SiC junction and a strongly enhanced current injection for MoS2/n+ SiC one. Thermionic emission is found the dominant mechanism ruling forward current in MoS2/n− SiC diodes, with an effective barrier ΦB= (1.04±0.09) eV. Instead, the significantly lower effective barrier ΦB= (0.31±0.01) eV and a temperature-dependent ideality factor for MoS2/n+ SiC junctions is explained by thermionic-field-emission through the thin depletion region of n+ doped SiC. The scalability of PLD MoS2 deposition and the electronic transport tunability by implantation doping of SiC represents key steps for industrial development of MoS2/SiC devices.

Ferritin nanoparticles play many important roles in theranostic and bioengineering applications and have been successfully used as nanovectors for the targeted delivery of drugs due to their ability to specifically bind the transferrin receptor (TfR1, or CD71). They can be either genetically or chemically modified for encapsulating therapeutics or probes in their inner cavity. Here, we analyzed a new engineered ferritin nanoparticle, made of the H chain mouse ferritin (HFt) fused with a specific lanthanide binding tag (LBT). The HFt-LBT has one high affinity lanthanide binding site per each of the 24 subunits and a tryptophane residue within the tag that acts as an antenna able to transfer the energy to the lanthanide ions via a LRET process. In this study, among lanthanides, we selected europium for its red emission that allows to reduce overlap with tissue auto-fluorescence. Steady state emission measurements and time-resolved emission spectroscopy have been employed to investigate the interaction between the HFt-LBT and the Eu

Carbon dots (CDs) are a family of fluorescent nanoparticles displaying a wide range of interesting properties, which make them attractive for potential applications in different fields like bioimaging, photocatalysis, and many others. However, despite many years of dedicated studies, wide variations exist in the literature concerning the reported photostability of CDs, and even the photoluminescence mechanism is still unclear. Furthermore, an increasing number of recent studies have highlighted the photobleaching (PB) of CDs under intense UV or visible light beams. PB phenomena need to be fully addressed to optimize practical uses of CDs and can also provide information on the fundamental mechanism underlying their fluorescence. Moreover, the lack of systematic studies comparing several types of CDs displaying different fluorescence properties represents another gap in the literature. In this study, we explored the optical properties of a full palette of CDs displaying a range from blue to red emissions, synthesized using different routes and varying precursors. We investigated the photostability of different CDs by observing in situ their time-resolved fluorescence degradation or optical absorption changes under equivalent experimental conditions and laser irradiation. The results about different PB kinetics clearly indicate that even CDs showing comparable emission properties may exhibit radically different resistances to PB, suggesting systematic connections between the resistance to PB, the characteristic spectral range of emission, and CD quantum yields. To exploit the PB dynamics as a powerful tool to investigate CD photophysics, we also carried out dedicated experiments in a partial illumination geometry, allowing us to analyze the recovery of the fluorescence due to diffusion. Based on the experimental results, we conclude that the nature of the CD fluorescence cannot be solely ascribable to small optically active molecules free diffusing in solution, contributing to shed light on one of the most debated issues in the photophysics of CDs.

International audience; Mechanical exfoliation assisted by gold is applied to obtain good quality large lateral size single-layer MoS2. The effects of 2.5 MeV electron irradiation are investigated at room temperature on structural and electronic features by Raman and microluminescence spectroscopy. The exciton recombination emission in the direct bandgap of single-layer MoS2 is affected during irradiation starting from the minimum explored dose of 1 kGy. At higher doses, Raman bands show no relevant modifications whereas the exciton emission is quenched, suggesting that irradiation-induced point defects affect exciton dynamics.

We investigated the interaction processes between high intensity femtosecond ultraviolet laser pulses and amorphous silica, leading to permanent refractive-index changes that are at the basis of advanced manufacturing for photonics devices. The experiment, carried out as a function of the laser power, improves our understanding on the strong-field ionization process by the monitoring of the 1.9 eV and 2.65 eV emissions, related to nonbridging oxygen hole centers and self-trapped exciton, respectively, induced in the exposed glass region. Our results clearly proved that the UV laser light band-to-band absorption is allowed in the multiphoton ionization limit, whose consecutive relaxation leads to the generation of these photoluminescence (PL) signatures. Furthermore, we coupled the online PL investigation with post mortem analysis of the irradiated volume through phase contrast microscopy, Raman and steady state PL, providing a complete view of the silica-femtosecond laser interaction.

Very recent red-emissive carbon nanodots (CDs) have shown potential as near-infrared converting tools to produce local heat useful in cancer theranostics. Besides, CDs seem very appealing for clinical applications combining hyperthermia, imaging, and drug delivery in a single platform capable of selectively targeting cancer cells. However, CDs still suffer from dramatic dot-to-dot variability issues such that a rational design of their structural, optical, and chemical characteristics for medical applications has been impossible so far. Herein, we report for the first time a simple and highly controllable layer-by-layer synthesis of biotin-decorated CDs with monodisperse size distribution, well established polymeric shell thickness, and degree of surface functionalization, endowed with strong red luminescence and the ability to convert NIR light into heat. These CDs, henceforth named CDs-PEG-BT, consist of a carbonaceous core passivated with biotin-terminated PEG2000 chains, which we demonstrate as active targeting groups to recognize cancer cells. The CDs-PEG-BT are designed to efficiently incorporate a high amount of anticancer drugs such as irinotecan (16-28%) and to act as NIR-activated nanoheaters capable of triggering local hyperthermia and massive drug release inside tumors, thus provoking sudden and efficient tumor death. The potential of the irinotecan-loaded CDs-PEG-BT (CDs-PEG-BT@IT) in fluorescence imaging was studied on 2D cultures and on complex 3D spheroids mimicking in vivo tumor architectures, showing their capability of selectively entering cancer cells through biotin receptors overexpressed in cell membranes. The efficient anticancer effect of these CDs was thoroughly assessed on multicellular 3D spheroids and patient organoids (tumor-on-a-dish preclinical models) to predict the drug response in humans in view of personalized medicine applications. CDs-PEG-BT@IT have a smart combination of properties, which pave the way to their real-world use as anticancer theranostic agents for image-guided photothermal applications.

Energy consumption in the world is increasing more and more due to the huge energy request coming from emerging countries such as China, India, etc. To face the challenge of sustainability, a solution may be the use of solar energy, since it is the most abundant renewable energy source on Earth. The electromagnetic energy coming from the Sun can be converted into usable energy (electricity) by solar cells, whose conversion efficiency is continuously increasing due to scientific and technological progress. The proposed activity is thought to be carried out with secondary as well as high school students to allow teachers to discuss sustainability issues, and to provide students with an introductory view into modern physics aspects (quantization of energy levels), quantum mechanics (semi-conductor band energies), and radiation-matter interaction. Furthermore, cutting-edge research in physics can reach school students, increasing their interest in scientific studies.

Carbon nanodots (CDs) are a new class of carbon-based nanoparticles endowed with photoluminescence, high specific surface area, and good photothermal conversion, which have spearheaded many breakthroughs in medicine, especially in drug delivery and cancer theranostics. However, the tight control of their structural, optical, and biological properties and the synthesis scale-up have been very difficult so far. Here, we report for the first time an efficient protocol for the one-step synthesis of decagram-scale quantities of N,S-doped CDs with a narrow size distribution, along with a single nanostructure multicolor emission, high near-infrared (NIR) photothermal conversion efficiency, and selective reactive oxygen species (ROS) production in cancer cells. This allows achieving targeted and multimodal cytotoxic effects (i.e., photothermal and oxidative stresses) in cancer cells by applying biocompatible NIR laser sources that can be remotely controlled under the guidance of fluorescence imaging. Hence, our findings open up a range of possibilities for real-world biomedical applications, among which is cancer theranostics. In this work, indocyanine green is used as a bidentate SOx donor which has the ability to tune surface groups and emission bands of CDs obtained by solvothermal decomposition of citric acid and urea in N,N-dimethylformamide. The co-doping implies various surface states providing transitions in the visible region, thus eliciting a tunable multicolor emission from blue to red and excellent photothermal efficiency in the NIR region useful in bioimaging applications and image-guided anticancer phototherapy. The fluorescence self-tracking capability of SOx-CDs reveals that they can enter cancer cells more quickly than healthy cell lines and undergo a different intracellular fate after cell internalization. This could explain why sulfur doping entails pro-oxidative activities by triggering more ROS generation in cancer cells when compared to healthy cell lines. We also find that oxidative stress can be locally enhanced under the effects of a NIR laser at moderate power density (2.5 W cm-2). Overall, these findings suggest that SOx-CDs are endowed with inherent drug-independent cytotoxic effects toward cancer cells, which would be selectively enhanced by external NIR light irradiation and helpful in precision anticancer approaches. Also, this work opens a debate on the role of CD surface engineering in determining nanotoxicity as a function of cell metabolism, thus allowing a rational design of next-generation nanomaterials with targeted anticancer properties.

We address the enhancement of orange-light luminescence of Mn-doped zinc sulfide nanoparticles (NPs) induced by exposure to UV light. Ultrafine ZnS:Mn NPs are prepared by microwave-assisted crystal growth in ethanol, without adding any dispersant agents. When exposed to UV light, their orange emission intensity undergoes a strong increase. This effect is observed when the NPs are deposited as a thin layer on a transparent substrate or dispersed in an ethanolic suspension. Such a feature was already observed on polymer- or surfactant-coated ZnS:Mn NPs and explained as a passivation effect. In this study, by coupling X-ray photoelectron, Fourier transform infrared, and electron paramagnetic resonance spectroscopy, we establish that this photoactivated luminescence is rather the consequence of lattice-strain effects. Indeed, our data show that UV irradiation in air promotes surface oxidation, replacing the outer sulfide layer with a sulfate one. The mismatch between the resulting outer crystallographic metal sulfate lattice and the inner sulfide one induces mechanical strains on the latter, thus partially relaxing the selection rules controlling the electronic transition from the 4T1 to the 6A1 molecular states of [MnS4]6- emitting centers. These results are relevant because they shed light on the long controversial discussions on the origin of the photoactivated phosphorescence in such systems.

Due to its unique properties, amorphous silicon dioxide (a-SiO2) or silica is a key material in many technological fields, such as high-power laser systems, telecommunications, and fiber optics. In recent years, major efforts have been made in the development of highly transparent glasses, able to resist ionizing and non-ionizing radiation. However the widespread application of many silica-based technologies, particularly silica optical fibers, is still limited by the radiation-induced formation of point defects, which decrease their durability and transmission efficiency. Although this aspect has been widely investigated, the optical properties of certain defects and the correlation between their formation dynamics and the structure of the pristine glass remains an open issue. For this reason, it is of paramount importance to gain a deeper understanding of the structure–reactivity relationship in a-SiO2 for the prediction of the optical properties of a glass based on its manufacturing parameters, and the realization of more efficient devices. To this end, we here report on the state of the most important intrinsic point defects in pure silica, with a particular emphasis on their main spectroscopic features, their atomic structure, and the effects of their presence on the transmission properties of optical fibers.

The bright photoluminescence of surface-functionalized carbon nanoparticles, known as carbon nanodots (CDs), has been studied for more than a decade because of its fundamental photo-physical interest and strong technological potential. However, the essential nature of the electronic states involved in their typical light emission remains very elusive. Here, we provide conclusive evidence that surface carboxylic moieties are the key to CD fluorescence. The synergy of nanosecond and femtosecond optical studies, cryogenic fluorescence, computational investigations and chemical engineering of a strategically chosen model CD system, allows to demonstrate that their visible-light transitions are due to the electron transfer from nitrogen atoms of the core to specific charge trap states strongly localized on –COOH surface groups. These results clarify a long-standing open problem in the photo-physics of carbon dots, and help to establish more solid foundations for the understanding of their optical response.

Carbon quantum dots (CQDs) are a new class of carbon-rich materials with a range of unique optical and structural properties. They can be defined as carbon nanoparticles, with sizes in the range of 1–10 nm, displaying absorption and emission activities in the UV-VIS range. Depending on the structure, CQDs display a wide variability of properties, which provides the possibility of finely tuning them for several applications. The great advantages of CQDs are certainly the ease of synthesis, non-toxicity, and the strong interactions with the surrounding environment. Based on this, CQDs are especially promising as selective chemosensors. The present study reports on carbon quantum dots synthesized with a top-down (TD) approach, and characterized by different optical, spectroscopic, and morphological techniques to identify the selectivity for metal ions belonging to the first transition series. In particular, the study focuses on the interaction between two samples, namely TD and TDA, featuring different surface functionalization, and heavy metal ions. Their sensing towards Co2+, Cu2+, Fe3+, Zn2+, and Ni2+ has been tested by fluorescence (PL), steady state absorption spectroscopy, and time-resolved PL spectroscopy, in order to determine the fluorescence quenching. We found a PL quenching in the presence of concentrations of metal salts starting from 0.5 µM, and a selectivity towards the interacting ions, depending on CQDs’ surface features paving the way for their use for sensing.

Funding Information: This work was carried out under the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), Academy of Finland's Centre of Excellence in Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland (No. 321443, 328942, 308647, and 318891) and Photonic Research and Innovation (PREIN) as well as FinnCERES flagships. L.F. and X.C. thanks for support from CSC (IT Center for Science, Finland) for providing computation resources. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC). | openaire: EC/H2020/742829/EU//DRIVEN Ultra-small luminescent gold nanoclusters (AuNCs) have gained substantial interest owing to their low photobleaching and high biocompatibility. While the substitution of silver for gold at the central core of AuNCs has shown significant augmentation of photoluminescence with enhanced photostability, selective replacement of the central atom by silver is, however, energetically inhibited. Herein, a new strategy for in situ site-selective Ag-doping exclusively at the central core of AuNCs using sulphated colloidal surfaces as the templates is presented. This approach exceedingly improves the photoluminescence quantum efficiency of AuNCs by eliminating nonradiative losses in the multi-step relaxation cascade populating the emissive state. Density functional theory predicts the mechanism of specific doping at the central core, endorsing the preferential bonding between Ag+ ions and sulphates in water. Finally, the generic nature of the templating concept to allow core-specific doping of nanoclusters is unraveled.

The gold-assisted exfoliation is a very effective method to produce large-area ($cm^2$-scale) membranes of molybdenum disulfide ($MoS_2$) for electronics. However, the strong $MoS_2/Au$ interaction, beneficial for the exfoliation process, has a strong impact on the vibrational and light emission properties of $MoS_2$. Here, we report an atomic force microscopy (AFM), micro-Raman ($\mu-R$) and micro-Photoluminescence ($\mu-PL$) investigation of $MoS_2$ with variable thickness exfoliated on Au and subsequently transferred on an $Al_2O_3/Si$ substrate. The $E_{2g}$ - $A_{1g}$ vibrational modes separation $\Delta\mu$ (typically used to estimate $MoS_2$ thickness) exhibits an anomalous large value ($\Delta\mu=21.2 cm^{-1}$) for monolayer (1L) $MoS_2$ on Au as compared to the typical one ($\Delta\mu=18.5 cm^{-1}$) measured on 1L $MoS_2$ on $Al_2O_3/Si$. Such substrate-related differences, explained in terms of tensile strain and p-type doping arising from the $MoS_2/Au$ interaction, were found to gradually decrease while increasing the number of $MoS_2$ layers. Furthermore, $\mu-PL$ spectra for 1L $MoS_2$ on Au exhibit a strong quenching and an overall red-shift of the main emission peak at 1.79 eV, compared to the 1.84 eV peak for 1L $MoS_2$ on $Al_2O_3$. After PL spectra deconvolution, such red shift was explained in terms of a higher trion/exciton intensity ratio, probably due to the higher polarizability of the metal substrate, as well as to the smaller equilibrium distance at $MoS_2/Au$ interface., Comment: 14 pages, 4 figures

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 MoS

Financial support by PJ-RIC-FFABR_2017 and the EPSRC grant EPSRC industrial CASE award (grant EP/N50936X/1) are acknowledged. The research programme Nanoporous materials (P1-0021) financially supported by Slovenian Research Agency (ARRS) is acknowledged as well. Metal-organic frameworks (MOFs) are promising materials for many potential applications, spacing from gas storage to catalysis. However, the powder form of which they are generally made is not suitable, mainly because of the low packing density. Powder compaction is therefore necessary, but also challenging because of their typical mechanical fragility. Indeed, generally, they undergo irreversibly damages upon densification processes, for example partially or totally loosing microporosity and catalytic activity. In this work, we deeply study the compaction effects on the flexible Cu(II)-based MOF STAM-17-OEt (Cu(C10O5H8)1.6 H2O), whose chemical composition is close to that of HKUST-1, obtaining that it is, by contrast, extremely suitable for mechanical compaction processes with pressures up to 200 MPa, which increase its packing density, its catalytic activity, and preserve porosity, flexibility and water stability, characteristics of STAM-17-OEt. The results are supported by many experimental techniques including EPR spectroscopy, PXRD diffraction, CO2 isotherms studies and catalytic tests. Publisher PDF

High-concentration photovoltaic (HCPV) systems are one of the most promising technologies for the generation of renewable energy with high-conversion efficiency. Their development is still at an early stage, but the possibility of integrating high-concentration systems into buildings offers new opportunities to achieve the net-zero-energy building goal. Herein, the optical and energetic performance of a hybrid daylighting−HCPV prototype based on pure- or doped-silica optical fibers (OFs) to guide 2000× concentrated sunlight inside the buildings is evaluated. There, the light can either be used to illuminate interior spaces or projected on solar cells to generate electricity. The system equipped with a single 400 μm core-diameter OF is demonstrated to achieve a total efficiency of 15% and an optical efficiency of 45%.

Carbon nanodots (CDs) are a new class of fluorescent carbon-based nanomaterials characterized by a plethora of morphologies and sizes. Among these, we can include two different types of CDs, namely, graphitic and diamond-like. This wide range of structures opens up the possibility to design different CDs, with tunable optical properties accordingly to the synthesis method and precursors used. We prepared two different CDs following a bottom-up approach by thermally induced decomposition of organic precursors (namely, citric acid and urea in different molar ratios), and using purification by Size Exclusion Chromatography (SEC). Obtained CDs were characterized by Raman, absorption and fluorescence (PL) spectroscopies to understand structural and optical properties, and by atomic force microscopy (AFM) to elucidate morphology. They feature graphitic and diamond-like carbon structures with highly efficient visible emissions. Their sensing towards Cd and Hg heavy metals has been tested by PL experiments. We found a PL quenching in the presence of concentrations of metal salts starting from 0.5 μM and a selectivity towards the interacting ions, depending on the CDs structure, enabling using them for sensing. Furthermore, preliminary experiments suggest that these dots can also be used in principle as sensors of common pesticides. Considering the advantages of carbon dots with respect to other nanomaterials, such as non-toxicity, low cost and ease of synthesis, we consider these results to be very promising in view of exploiting the optical response of carbon dots to fabricate in the near future a variety of pollutant-sensing devices.

We report a set of femtosecond (fs) transient absorption (TA) measurements following the dynamics of the so-called nonbridging oxygen hole center in silica, a model color center in wide bandgap amorphous solids, characterized by a very large Stokes shift between the UV excitation and its associated red emission at 1.9 eV. The changes in the TA spectrum were probed in the UV-visible range at various delays after photoexcitation and analyzed as a function of the UV excitation energy, in single-photon absorption conditions. The combination of the experiments helps to clarify the defect photocycle, highlighting how TA measurements with tunable UV excitation could represent a powerful tool to investigate the dynamics of color centers embedded in transparent materials. © 2021 Optical Society of America

The nature of the radiation-induced point defects in amorphous silica is investigated through online photoluminescence (PL) under high intensity ultrashort laser pulses. Using 1030 nm femtosecond laser pulses with a repetition rate of 1 kHz, it is possible to study the induced color centers through their PL signatures monitored during the laser exposure. Their generation is driven by the nonlinear absorption of the light related to the high pulse peak powers provided by femtosecond laser, allowing to probe the optical properties of the laser exposed region. The experiment is conducted as a function of the laser pulse power in samples with different OH contents. The results highlight the different interaction regimes attained by varying the irradiation conditions for various chemical compositions. Moreover, the online measurements are combined with postmortem characterization of the damaged area, via phase contrast microscopy, Raman and steady-state PL spectroscopies, highlighting the potential of these online femtosecond tests to provide additional knowledge to the postmortem technique ones.

In this paper we demonstrated the thermal Atomic Layer Deposition (ALD) growth at 250 {\deg}C of highly homogeneous and ultra-thin ($\approx$ 3.6 nm) $Al_2O_3$ films with excellent insulating properties directly onto a monolayer (1L) $MoS_2$ membrane exfoliated on gold. Differently than in the case of 1L $MoS_2$ supported by a common insulating substrate ($Al_2O_3/Si$), a better nucleation process of the high-k film was observed on the 1L $MoS_2/Au$ system since the ALD early stages. Atomic force microscopy analyses showed a $\approx 50\%$ $Al_2O_3$ surface coverage just after 10 ALD cycles, its increasing up to $>90\%$ (after 40 cycles), and an uniform $\approx$ 3.6 nm film, after 80 cycles. The coverage percentage was found to be significantly reduced in the case of 2L $MoS_2/Au$, indicating a crucial role of the interfacial interaction between the aluminum precursor and $MoS_2/Au$ surface. Finally, Raman spectroscopy and PL analyses provided an insight about the role played by the tensile strain and p-type doping of 1L $MoS_2$ induced by the gold substrate on the enhanced high-k nucleation of $Al_2O_3$ thin films. The presently shown high quality ALD growth of high-k $Al_2O_3$ dielectrics on large area 1L $MoS_2$ induced by the Au underlayer can be considered of wide interest for potential device applications based on this material system., Comment: 21 pages, 6 figures

The transmission performances of pure- and doped-silica (a-SiO2) optical fibres are compared during the exposure to a high-power broadband light source approximating the solar spectrum. From the Gaussian decomposition of the attenuation spectra, we found that Al- and P-doped fibres show a fast solarisation effect which leads to transmission degradation in the ultraviolet-visible range. Similarly, Ge-doped fibres undergo photoinduced colour-centre formation which, however, does not prevent visible-light propagation. One of the two tested pure-silica fibres results completely unaffected by light exposure whereas the other shows an absorption band probably due to the presence of chlorine impurities in the silica matrix.The reported results demonstrate the possibility of using commercial Ge-doped and pure-silica fibres for indoor lighting applications and fibre-based photovoltaic devices.

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 (, A.S. was supported by the “L’Oréal Italia Per le Donne e la Scienza” Program (17th edition). A.S. and F.M. thank the Italian Ministry of University and Research (MUR) for project PRIN2017 “CANDL2”, grant number 2017W75RAE. G.G. thanks the Portuguese Science Foundation (FCT) for Programme Stimulus of Scientific EmploymentIndividual Support (CEECIND/01913/2017). We acknowledge funding received by the Karlsruhe Nano Micro Facility (KNMF)− proposal ID 2019-021025715., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

In this article, the charge trapping phenomena in Al2O3 thin films grown by atomic layer deposition (ALD) on AlGaN/GaN heterostructures have been studied by time-dependent capacitance–voltage (C-V) measurements as a function of temperature. In particular, monitoring the transient of the capacitance enabled us to estimate the maximum depth of the insulating layer interested by the negative charge trapping effect under our bias stress conditions and to determine a charge traps density in the bulk Al2O3 in the order of 3 × 1019 cm−3. A temperature dependent C-V analysis up to 150 °C demonstrated the presence of two competitive mechanisms that rule the electron capture and emission in the Al2O3 film, characterized by activations energies of 22 and 88 meV respectively. Photoluminescence analyses revealed the presence of oxygen-related point defects in the insulator with a concentration in the order of ∼1020 cm−3 envisaging that only a fraction of them is electrically active. The results are useful to establish the thermal stability of the trapping phenomena, and the possible application in real devices.

Carbon dots are a family of optically-active nanoparticles displaying a combination of useful properties that make them attractive for many applications in photonics and photochemistry. Despite the initial claims of high photostability of carbon dots even under prolonged illuminations, several recent studies have evidenced their photobleaching (PB) under UV light, detrimental for some applications. A study of the mechanism and dynamics of carbon dot PB can be considered a useful route to gather relevant information on the underlying photophysics of these nanoparticles, which is still widely debated. Here we report a study of the PB of carbon dots under UV light, conducted through optical experiments under well-controlled illumination conditions. In particular, the use of a laser as an irradiation source allows a precise control of the irradiated volume, and provides accurate estimates and control of the administered energy. Besides, our setup allows spectroscopic measurements to be carried out in situ at the irradiated site, thus allowing us to investigate in real time the progress of photobleaching effects through a time-resolved approach. Therefore, our experiments allow the precise kinetics of the undergoing PB process to be captured which is found to be significantly affected by disorder and photoselection effects. Furthermore, our study discloses several pieces of information on the nature of the main blue chromophore absorbing at 340 nm and emitting at 430 nm, and on its PB mechanism. We propose that the emissive units consist in small molecular-like chromophores adsorbed on carbon dot surfaces and are in a dynamical equilibrium with free diffusing molecules in solution. Their photobleaching proceeds in two distinct steps: in the first phase, linear absorption of UV photons rapidly converts the molecular surface chromophores into a non-emissive form, likely through an isomerization, causing the disappearance of the fluorescence properties but almost no changes in the optical absorption spectra. At higher fluences, a complete destruction of the optically-active centers is observed, which completely wipes out all the absorption features of surface chromophores and only leaves a fully carbonized, yet non-fluorescent, dot core.

We investigated the nature, optical properties, and decay kinetics of point defects causing large transient attenuation increase observed in silica-based optical fibers exposed to short duration and high-dose rate x-ray pulses. The transient radiation-induced attenuation (RIA) spectra of pure-silica-core (PSC), Ge-doped, F-doped, and Ge + F-doped optical fibers (OFs) were acquired after the ionizing pulse in the spectral range of [∼0.8–∼3.2] eV (∼1500–∼380 nm), from a few ms to several minutes after the pulse, at both room temperature (RT) and liquid nitrogen temperature (LNT). Comparing the fiber behavior at both temperatures better highlights the thermally unstable point defects contribution to the RIA. The transient RIA origin and decay kinetics are discussed on the basis of already-known defects absorbing in the investigated spectral range. These measurements reveal the importance of intrinsic metastable defects such as self-trapped holes (STHs), not only for PSC and F-doped fibers but also for germanosilicate optical fibers as clearly evidenced by our LNT measurements. Furthermore, our results show that fluorine co-doping seems to decrease the RIA related to the strain-assisted STHs absorption bands in both types of optical fibers. Regarding Ge-doped glasses, besides a description of the defects responsible of the RIA, highlighting the STHs' role in their transient response, we provide a clear correlation between the GeX and GeY centers’ kinetics. In conclusion, the presented results improve our understanding of the transient RIA origin in the ultraviolet and visible domains. The lack of knowledge about the defects causing the RIA in the near-infrared domain will require future studies.

Using solar radiation to fuel catalytic processes is often regarded as the solution to our energy needs. However, developing effective photocatalysts that are active under visible light has proven to be difficult, often due to the toxicity, instability, and high cost of suitable catalysts. We engineered a novel photoactive nanomaterial obtained by the spontaneous electrostatic coupling of carbon nanodots with [P2W18O62]6-, a molecular catalyst belonging to the class of polyoxometalates. While the former are used as photosensitizers, the latter was chosen for its ability to catalyze reductive reactions such as dye decomposition and water splitting. We find the electron transfer within the nanohybrid to be so efficient that a charge-separated state is formed within 120 fs from photon absorption. These results are a cornerstone in the engineering of a new class of nanodevices, which are nontoxic, are inexpensive, and can carry out solar-driven catalytic processes.

Graphene (Gr)&mdash, a single layer of two-dimensional sp2 carbon atoms&mdash, and Carbon Dots (CDs)&mdash, a novel class of carbon nanoparticles&mdash, 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&ndash, 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.