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Metal-halide perovskites are revolutionizing the world of X-ray detectors, due to the development of sensitive, fast, and cost-effective devices. Self-powered operation, ensuring portability and low power consumption, has also been recently demonstrated in both bulk materials and thin films. However, the signal stability and repeatability under continuous X-ray exposure has only been tested up to a few hours, often reporting degradation of the detection performance. Here it is shown that self-powered direct X-ray detectors, fabricated starting from a FAPbBr3 submicrometer-thick film deposition onto a mesoporous TiO2 scaffold, can withstand a 26-day uninterrupted X-ray exposure with negligible signal loss, demonstrating ultra-high operational stability and excellent repeatability. No structural modification is observed after irradiation with a total ionizing dose of almost 200 Gy, revealing an unexpectedly high radiation hardness for a metal-halide perovskite thin film. In addition, trap-assisted photoconductive gain enabled the device to achieve a record bulk sensitivity of 7.28 C Gy-1 cm-3 at 0 V, an unprecedented value in the field of thin-film-based photoconductors and photodiodes for "hard" X-rays. Finally, prototypal validation under the X-ray beam produced by a medical linear accelerator for cancer treatment is also introduced.
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In the present work, an insight on the morpho/structural properties of semitransparent organic devices for buildings' integrated photovoltaics is presented, and issues related to interface and bulk stability are addressed. The organic photovoltaic (OPV) cells under investigation are characterized by a blend of PM6:Y6 as a photo-active layer, a ZnO ETL (electron transporting layer), a HTL (hole transporting layer) of HTL-X and a transparent electrode composed by Ag nanowires (AgNWs). The devices' active nanomaterials, processed as thin films, and their mutual nanoscale interfaces are investigated by a combination of in situ Energy Dispersive X-ray Reflectometry (EDXR) and ex situ Atomic Force Microscopy (AFM), X-ray Diffraction (XRD) and micro-Raman spectroscopy. In order to discriminate among diverse concomitant aging pathways potentially occurring upon working conditions, the effects of different stress factors were investigated: light and temperature. Evidence is gained of an essential structural stability, although an increased roughness at the ZnO/PM6:Y6 interface is deduced by EDXR measurements. On the contrary, an overall stability of the system subjected to thermal stress in the dark was observed, which is a clear indication of the photo-induced origin of the observed degradation phenomenon. Micro-Raman spectroscopy brings light on the origin of such effect, evidencing a photo-oxidation process of the active material in the device, using hygroscopic organic HTL, during continuous illumination in ambient moisture conditions. The process may be also triggered by a photocatalytic role of the ZnO layer. Therefore, an alternative configuration is proposed, where the hygroscopic HTL-X is replaced by the inorganic compound MoOx. The results show that such alternative configuration is stable under light stress (solar simulator), suggesting that the use of Molybdenum Oxide, limiting the photo-oxidation of the bulk PM6:Y6 active material, can prevent the cell from degradation.
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Thin films based on scandium oxide (Sc2O3) were deposited on silicon substrates to investigate the thickness effect on the reduction of work function. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), energy dispersive X-ray reflectivity (EDXR), atomic force microscopy (AFM), and ultraviolet photoelectron spectroscopy (UPS) measurements were performed on the films deposited by electron-beam evaporation with different nominal thicknesses (in the range of 2-50 nm) and in multi-layered mixed structures with barium fluoride (BaF2) films. The obtained results indicate that non-continuous films are required to minimize the work function (down to 2.7 eV at room temperature), thanks to the formation of surface dipole effects between crystalline islands and substrates, even if the stoichiometry is far from the ideal one (Sc/O = 0.38). Finally, the presence of BaF2 in multi-layered films is not beneficial for a further reduction in the work function.
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One-monolayer (ML) (thin) and 5-ML (thick) Si films were grown on the α-phase Si(111)â3 × â3R30°-Bi at a low substrate temperature of 200 °C. Si films have been studied in situ by reflection electron energy loss spectroscopy (REELS) and Auger electron spectroscopy, as a function of the electron beam incidence angle α and low-energy electron diffraction (LEED), as well as ex situ by grazing incidence X-ray diffraction (GIXRD). Scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS) were also reported. The REELS spectra, taken at the Si K absorption edge (~1.840 KeV), reveal the presence of two distinct loss structures attributed to transitions 1sâπ* and 1sâσ* according to their intensity dependence on α, attesting to the sp2-like hybridization of the silicon valence orbitals in both thin and thick Si films. The synthesis of a silicon allotrope on the α-phase of Si(111)â3 × â3R30°-Bi substrate was demonstrated by LEED patterns and GIXRD that discloses the presence of a Si stack of 3.099 (3) Å and a â3 × â3 unit cell of 6.474 Å, typically seen for multilayer silicene. STM and STS measurements corroborated the findings. These measurements provided a platform for the new â3 × â3R30° Si allotrope on a Si(111)â3 × â3 R30°-Bi template, paving the way for realizing topological insulator heterostructures from different two-dimensional materials, Bi and Si.
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The use of solution processes to fabricate perovskite solar cells (PSCs) represents a winning strategy to reduce capital expenditure, increase the throughput, and allow for process flexibility needed to adapt PVs to new applications. However, the typical fabrication process for PSC development to date is performed in an inert atmosphere (nitrogen), usually in a glovebox, hampering the industrial scale-up. In this work, we demonstrate, for the first time, the use of double-cation perovskite (forsaking the unstable methylammonium (MA) cation) processed in ambient air by employing potassium-doped graphene oxide (GO-K) as an interlayer, between the mesoporous TiO2 and the perovskite layer and using infrared annealing (IRA). We upscaled the device active area from 0.09 to 16 cm2 by blade coating the perovskite layer, exhibiting power conversion efficiencies (PCEs) of 18.3 and 16.10% for 0.1 and 16 cm2 active area devices, respectively. We demonstrated how the efficiency and stability of MA-free-based perovskite deposition in air have been improved by employing GO-K and IRA.
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Organic-inorganic lead halide perovskite has recently emerged as an efficient absorber material for solution process photovoltaic (PV) technology, with certified efficiency exceeding 25%. The development of low-temperature (LT) processing is a challenging topic for decreasing the energy payback time of perovskite solar cell (PSC) technology. In this context, the LT planar n-i-p architecture meets all the requirements in terms of efficiency, scalability, and processability. However, the long-term stability of the LT planar PSC under heat and moisture stress conditions has not been carefully assessed. Here, a detailed study on thermal and moisture stability of large-area (1 cm2) LT planar PSCs is presented. In particular, the key role in thermal stability of potassium iodide (KI) insertion in the perovskite composition is demonstrated. It is found that defect passivation of triple-cation perovskite by KI doping inhibits the halide migration induced by thermal stress at 85 °C and delays the formation of degradation subproducts. T80, defined as the time when the cell retains 80% of initial efficiency, is evaluated both for reference undoped devices and KI-doped ones. The results show that T80 increases 3 times when KI doping is used. Moreover, an HTL-free architecture where the Au top electrode is replaced with low-T screen-printable carbon paste is proposed. The combination of the carbon-based HTL-free architecture and KI-doped perovskite permits T80 to increase from 40 to 414 h in unsealed devices.
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Citrate-capped gold nanoparticles (AuNPs) were functionalized with three distinct antitumor gold(III) complexes, e.g., [Au(N,N)(OH)2][PF6], where (N,N)=2,2'-bipyridine; [Au(C,N)(AcO)2], where (C,N)=deprotonated 6-(1,1-dimethylbenzyl)-pyridine; [Au(C,N,N)(OH)][PF6], where (C,N,N)=deprotonated 6-(1,1-dimethylbenzyl)-2,2'-bipyridine, to assess the chance of tracking their subcellular distribution by atomic force microscopy (AFM), and surface enhanced Raman spectroscopy (SERS) techniques. An extensive physicochemical characterization of the formed conjugates was, thus, carried out by applying a variety of methods (density functional theory-DFT, UV/Vis spectrophotometry, AFM, Raman spectroscopy, and SERS). The resulting gold(III) complexes/AuNPs conjugates turned out to be pretty stable. Interestingly, they exhibited a dramatically increased resonance intensity in the Raman spectra induced by AuNPs. For testing the use of the functionalized AuNPs for biosensing, their distribution in the nuclear, cytosolic, and membrane cell fractions obtained from human lymphocytes was investigated by AFM and SERS. The conjugates were detected in the membrane and nuclear cell fractions but not in the cytosol. The AFM method confirmed that conjugates induced changes in the morphology and nanostructure of the membrane and nuclear fractions. The obtained results point out that the conjugates formed between AuNPs and gold(III) complexes may be used as a tool for tracking metallodrug distribution in the different cell fractions.
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Antineoplásicos/química , Oro/química , Nanopartículas del Metal/química , Nanopartículas del Metal/ultraestructura , Microscopía de Fuerza Atómica , Espectrometría Raman , HumanosRESUMEN
We report new findings on multilayer silicene grown on Si(111)â3 × â3 R30°-Ag template, after the recent first compelling experimental evidence of its synthesis. Low-energy electron diffraction, reflection high-energy electron diffraction, and energy-dispersive grazing incidence X-ray diffraction measurements were performed to show up the fingerprints of â3 × â3 multilayer silicene. Angle-resolved photoemission spectroscopy displayed new features in the second surface Brillouin zone, attributed to the multilayer silicene on Si(111)â3 × â3 R30°-Ag. Band-structure dispersion theoretical calculations performed on a model of three honeycomb stacked layers, silicene grown on Si(111)â3 × â3 R30°-Ag surface confirm the experimental results.
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Among the hybrid metal-organic perovskites for photovoltaic applications, FAPbI3 (FAPI) has the best performance regarding efficiency and the worst regarding stability, even though the reports on its stability are highly contradictory. In particular, since at room temperature the cubic α phase, black and with high photovoltaic efficiency, is metastable against the yellow hexagonal δ phase, it is believed that α-FAPI spontaneously transforms into δ-FAPI within a relatively short time. We performed X-ray diffraction and thermogravimetric measurements on loose powder of FAPI, and present the first complete dielectric and anelastic spectra of compacted FAPI samples under various conditions. We found that α-FAPI is perfectly stable for at least 100 days, the duration of the experiments, unless extrinsic factors induce its degradation. In our tests, degradation was detected after exposure to humidity, strongly accelerated by grain boundaries and the presence of δ phase, but it was not noticeable on the loose powder kept in air under normal laboratory illumination. These findings have strong implications on the strategies for improving the stability of FAPI without diminishing its photovoltaic efficiency through modifications of its composition.
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The Raman spectral features from spinal cord tissue sections of transgenic, ALS model mice and non-transgenic mice were compared using 457 nm excitation line, profiting from the favourable signal intensity obtained in the molecular fingerprint region at this wavelength. Transverse sections from four SOD1G93A mice at 75 days and from two at 90 days after birth were analysed and compared with sections of similarly aged control mice. The spectra acquired within the grey matter of tissue sections from the diseased mice is markedly different from the grey matter signature of healthy mice. In particular, we observe an intensity increase in the spectral windows 450-650 cm-1 and 1050-1200 cm-1, accompanied by an intensity decrease in the lipid contributions at ~1660 cm-1, ~1440 cm-1 and ~1300 cm-1. Axons demyelination, loss of lipid structural order and the proliferation and aggregation of branched proteoglycans are related to the observed spectral modifications. Furthermore, the grey and white matter components of the spinal cord sections could also be spectrally distinguished, based on the relative intensity of characteristic lipid and protein bands. Raman spectra acquired from the white matter regions of the SOD1G93A mice closely resembles those from control mice.
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Esclerosis Amiotrófica Lateral/diagnóstico por imagen , Esclerosis Amiotrófica Lateral/patología , Espectrometría Raman , Médula Espinal/diagnóstico por imagen , Médula Espinal/patología , Animales , Sustancia Gris/patología , Ratones Endogámicos C57BL , Ratones Transgénicos , Procesamiento de Señales Asistido por Computador , Superóxido Dismutasa/genética , Sustancia Blanca/patologíaRESUMEN
Enhancement of the stability of bulk heterojunction (BHJ) organic photovoltaic (OPV) devices is reported by the addition of surfactant-free aluminum (Al) nanoparticles (NPs) into the photoactive layer. The universality of the effect is demonstrated for two different BHJ systems, namely, the well-studied poly(3-hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as well as the high efficient poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]:[6,6]-phenyl-C71-butyric acid methyl ester (PCDTBT:PC71BM). It is shown that the lifetime of the devices with Al NPs, operating under continuous one-sun illumination in ambient conditions, is more than three times longer compared to the reference devices. Using complementary analytical techniques for in situ studies, we have explored the underlying mechanisms behind the observed stability improvement in the case of the P3HT:PCBM system. In particular, laser-induced fluorescence (LIF), photoluminescence decay and Fourier transform infrared (FTIR) spectroscopy experiments were performed and complemented with device degradation electrical measurements. It is found that the embedded Al NPs act as performance stabilizers, giving rise to enhanced structural stability of the active blend. Furthermore, it is revealed that the observed improvement can also be ascribed to NP-mediated mitigation of the photo-oxidation effect. This study addresses a major issue in OPV devices, that is, photoinduced stability, indicating that the exploitation of Al NPs could be a successful approach toward fabricating OPVs exhibiting long-term operating lifetimes.
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This study focuses on the crucial problem of the stability of organic photovoltaic (OPV) devices, aiming to shed light on the photo and thermal degradation mechanisms during prolonged irradiation under ambient conditions. For this purpose, the stability enhancement of bulk heterojunction OPV devices upon embedding surfactant free Au nanoparticles (NPs) into the photoactive layer is investigated by in situ time-resolved energy dispersive X-ray reflectometry (EDXR), photoluminescence (PL) and Raman spectroscopy as well as device degradation electrical measurements. It is shown that besides the improved cell efficiency attributed to plasmon absorption and scattering effects, the embedded NPs act as performance stabilizers, giving rise to enhanced structural stability and, in turn, to reduced photodegradation rate of the respective OPV devices. It is particularly clarified that, in addition to further stabilization of the polymer-fullerene blend, the observed improvement can be ascribed to a NP-mediated mitigation of the photooxidation effect at the cathode-active layer interface. Our work suggests the exploitation of surfactant free NPs to be a successful approach to address aging effects in OPV devices.
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The nanoscale organization of acetylcholinesterase (AChE) and of its polyclonal antibody immobilized on gold thin films was studied by means of Energy Dispersive X-ray Reflectometry (EDXR) and Atomic Force Microscopy (AFM). The macromolecules were alternatively deposited over a self-assembled monolayer (SAM) of N-hydroxysuccinimide esters of thioctic acid. The measurements, collected in situ at subsequent deposition stages of the device, gave information on the distribution of the macromolecules on the surface showing that both the proteins can bind covalently to the SAM. In addition to this, we demonstrated that the antigen-antibody reaction takes place when one of the two reactants is anchored to the surface.
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Acetilcolinesterasa/química , Anticuerpos Inmovilizados/química , Enzimas Inmovilizadas/química , Oro/química , Membranas Artificiales , Nanopartículas/química , Reacciones Antígeno-Anticuerpo , Microscopía de Fuerza Atómica , Propiedades de SuperficieRESUMEN
Carbonated hydroxyapatite (CHA)-coated titanium can find wide applications as bone substitute implant in bone and dental surgery and orthopedics, promoting osseointegration with a host bone and ensuring biocompatibility and bioactivity. In this work, carbonated hydroxyapatite films were prepared on titanium substrates by pulsed laser deposition at different substrate temperatures ranging from 30 to 750 degrees C. The properties of films were investigated by scanning electron microscopy, atomic force microscopy, energy-dispersive X-ray diffraction, and Fourier transform infrared spectroscopy. Vickers microhardness measurements of the composite film-substrate systems were performed, and the intrinsic hardness of films was separated from the composite hardness using a "law-of-mixtures" approach and taking into account the indentation size effect. The prepared CHA films are nearly stoichiometric with a Ca/P atomic ratio of 2.0-2.2. The films deposited in the 30-500 degrees C temperature range are about 9 microm thick, amorphous, having an average roughness of 60 nm. At higher temperature, 700-750 degrees C, the films are about 4 microm thick, show a finer surface morphology and an average roughness of 20 nm. At 750 degrees C the films are amorphous, whereas at 700 degrees C they are crystalline and textured along the (202) and (212) directions. The intrinsic hardness of the films increased with an increase in substrate temperature, being as low as 5 GPa at 30 degrees C and reaching a high value of 28 GPa at 700 degrees C. The rich information gained by the joint use of the mentioned techniques allowed a comprehensive characterization of this system.
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Sustitutos de Huesos/química , Carbono/química , Hidroxiapatitas/química , Calcio/química , Química Física/métodos , Rayos Láser , Ensayo de Materiales , Microscopía de Fuerza Atómica/métodos , Microscopía Electrónica de Rastreo/métodos , Fosfatos/química , Presión , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Temperatura , Titanio/química , Difracción de Rayos XRESUMEN
This review presents studies devoted to the description and comprehension of phenomena connected with the sensing behaviour towards NO(2) of films of two phthalocyanines, titanium bis-phthalocyanine and ruthenium phthalocyanine. Spectroscopic, conductometric, and morphological features recorded during exposure to the gas are explained and the mechanisms of gas-molecule interaction are also elucidated. The review also shows how X-ray reflectivity can be a useful tool for monitoring morphological parameters such as thickness and roughness that are demonstrated to be sensitive variables for monitoring the exposure of thin films of sensor materials to NO(2) gas.
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A combined ultrahigh vacuum scanning tunneling microscopy (STM-UHV) and energy dispersive X-ray diffractometry/reflectometry (EDXD/EDXR) study of the evolution of face-centered cubic (fcc) Pt layer growth on MgO(100) by pulsed laser deposition as a function of the process parameters such as deposition temperature and deposition duration has been carried out. The aim of this study is to define the best experimental conditions to obtain a controlled film deposition selective on the Pt growth direction (either [111] or [002]). The evolution of the Pt surface morphology as a function of the deposition temperature (T(dep)) from 300 to 700 degrees C has been studied with STM and ED techniques. Results show that the Pt surface, characterized at T(dep) = 300 degrees C by a 3D island morphology, evolves at higher temperatures to a morphology in which the original islands coexist with a distribution of orthogonal 2D stripes. The two features can be associated with the [111] and [002] Pt growth directions of the fcc phase, respectively. For T(dep) = 700 degrees C, the island morphology of the (111) face completely disappears, while the merging process of the (002) stripes reaches completion. The evolution of the morphology at T(dep) = 600 degrees C as a function of the deposition time and thickness has then been studied with STM-UHV, revealing an initial growth of mosaic-like 3D islands. These independent islands, already interconnected, expand along two orthogonal directions and, for longer deposition times, lead to the texture of orthogonal stripes. The EDXR characterization providing the morphological parameters of the films, i.e., thickness and roughness, confirms the above observation and quantifies the effect of such morphological changes on the surface roughness of the Pt film, an important parameter for applications of Pt films as underlayer in magnetic recording media.