In the present research, we successfully synthesized thin films of Cerium Oxide (CeO2) and Neodymium (Nd) doped CeO2 on both glass and ITO substrates using the chemical spray pyrolysis method. Their structural, morphological, optical and electrochemical properties were experimentally studied. X-ray diffraction analyses showed that all the layers exhibited the cubic fluorite phase characteristic of CeO2. Raman spectroscopy reveals a downward F2g band shift in all Nd3+-doped CeO2 films due to oxygen vacancies. The asymmetry and broadening of the Raman modes arise from the injection of Nd3+ ions in CeO2 thin films, which leads to variations in the presence of Ce3+ and oxygen vacancies. Additionally, the morphology of the films changes with different levels of Nd-doping. The UV-Vis-NIR spectra obtained in the wavelength scale between 300 nm and 1800 nm showed a noticeable reduction in the band gap from 3.46 eV to 3.30 eV. The cyclic voltammetry (CV) results indicate that the addition of Nd improves the ion storage capacities (ISC) of the cerium oxide thin film. Even after the intercalation/deintercalation of lithium ions, the doped cerium oxide thin films remain fully transparent. These significant findings broaden the potential applications of this oxide, particularly for electrochromic devices.

In this research, we explored the influence of varying concentrations of KOH electrolyte (0.5, 1, and 2M) on the electrochemical characteristics of Nickel Oxide (NiO) thin film. The deposition of NiO material onto glass and Fluor Tin Oxide (FTO) coated glass substrates was achieved through the chemical spray pyrolysis method. Subsequent examinations encompassed structural, morphological, optical, and electrochemical assessments, employing X-ray diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS), UV-VIS-NIR spectrophotometry, and cyclic voltammetry (CV), respectively. XRD analysis unveiled a polycrystalline cubic structure of NiO with a preference for orientation along the (111) plane. Raman spectroscopy confirmed the presence of the NiO phase, whereas SEM images depicted the emergence of interconnected nanograins with occasional minor cracks. EDS examination and elemental mapping further substantiated a homogeneous dispersion of elements. Optical analysis disclosed a band gap energy of 3.54 eV and an average transmittance of 71% in the visible range. Electrochemical analysis indicated that the specific capacitance reached its peak at [1M] (70 F. g−1). The [2M] electrolyte exhibited the highest optical modulation (29%), the most substantial charge density (Qi=9.5 mC/cm2), and the most favorable switching kinetics. However, the coloration efficiency slightly decreased from 30.94 cm2/C in [1M] to 30.47 cm2/C in the [2M] solution, despite these improvements.

In this study, the authors investigated the influence of hafnium doping on the properties of NiO thin films using the spray pyrolysis (SP) method. A comprehensive analysis was conducted to evaluate the structural, morphological, optical, and electrochemical characteristics of the deposited films. Techniques such as X-ray diffraction analysis (XRD), Raman spectroscopy, scanning electron microscopy (FESEM), energy dispersive analysis by X-ray (EDS), UV-Vis-NIR spectrophotometry, cyclic voltammetry (CV), and chronoamperometry (CA) were employed. XRD examination revealed that the NiO thin films exhibit a polycrystalline cubic phase, with a preferred orientation along the (111) plane. The successful integration of Hf ions into the NiO matrix was confirmed by the Raman spectrum. SEM images depicted the formation of dense and uniform nanograins on all film surfaces, free from any cracks. EDS analysis and elemental mapping indicated uniform and homogeneous distribution of Ni, O, and Hf elements across the films. The optical analysis suggested a decrease in the optical band gap energy from 3.54 eV to 3.49 eV with an increase in hafnium doping concentration. Electrochemical results revealed a continuous improvement in specific capacitance with Hf doping. The NHf6 sample reached 65 F. g(-1) at 5 mV s(-1), compared to 46 F. g(-1) at 5 mV s(-1) for the NHf0 sample. However, the NHf4 film exhibited the highest optical density variation (49%), shortest response times (t(b) = 3.58 s, t(c) = 4.67 s), and the largest coloration efficiency (63.39 cm(2)/C), indicating enhanced electrochromic performance at this Hf doping rate. These findings suggest that Hf-doped NiO holds promise as a candidate for use as a counter-electrode in electrochromic devices.

Cerium oxide nanostructured thin films, as well as their variants doped with Gadolinium (Gd), Neodymium (Nd) and Indium (In), were successfully deposited onto both glass and ITO substrates using the spray pyrolysis method. Their structural, morphological, optical, and electrochemical properties were then experimentally studied. X-ray diffraction (XRD) has confirmed the generation of a single -phase polycrystalline cubic fluorite structure of CeO 2 . The crystallite size and microstrain of the thin films were found to depend on the type of doping element. Red -shift, peak broadening, and asymmetry in the Raman mode (F 2 g ), as well as a red-shifted energy gap, were confirmed through Raman spectroscopy and UV - Vis - NIR analyses. SEM images reveal nanograin formation in all the films, while EDS analysis confirms the presence of the elements. The electrochemical measurements indicate that doping CeO 2 with Gd, Nd, and In enhances its electrochemical properties. Furthermore, the doped CeO 2 thin films maintain full transparency during the intercalation and deintercalation of Li + ions. Such pivotal findings broaden the potential applications of this oxide, particularly in supercapacitors and electrochromic devices.

Abstract Vanadium oxides have been investigated for their potential use in electrochemical supercapacitors due to their variable oxidation states yielding surface redox. However, its electrochemical performance is limited by its poor electronic and ionic conductivity. In an attempt to improve the electronic conductance and electrochemical performance of V2O5, (Mn, Zn) co-doped V2O5 is investigated. (Mn, Zn) (2, 2) wt% co-doped V2O5 provides the high specific capacitance, it achieves 23.72F/g at a scan rate of 5mV/s, and it is characterized by very low charge transfer resistance (301mΩ). At 2A/g current density, its power density and energy density are about 2520Wkg− 1, and 4.85Whkg− 1respectively. Because of its good electrochemical performance, (Mn, Zn) (2, 2) wt% co-doped V2O5 has great application prospects in supercapacitors.

In this work, planar heterojunction organic photovoltaic cells (PHJ-OPVs) based on alpha-sexithiophene (alpha-6T) and fullerene active materials were investigated. We have studied the effect of the hole transporting layer (HTL) on the performances of the PHJ-OPVs. The studied HTLs are molybdenum trioxide (MoO3), cuprous iodide CuI and MoO3 coupled with CuI (MoO3/CuI). The PHJ-OPVs were fabricated using the thermal evaporation/sublimation technique. The experimental study shows that double HTL MoO3/CuI, using 1.5 nm of CuI thickness, improves significantly the efficiency of the PHJ-OPVs compared with those with single HTLs. This enhancement is due to the fact that MoO3 contributes to the optimization of the holes collection and CuI causes significant influence on the nucleation and the growth of alpha-6T. CuI has led to spectacular modification of the structural properties of alpha-6T. When alpha-6T is deposited onto ITO/MoO3, the alpha-6T layers are amorphous, while they are crystallized into monoclinic crystalline structure with a laying down molecular orientation when they are deposited onto ITO/MoO3/CuI. The use of the double HTL and the optimization of the alpha-6T deposition parameters have led to an important improvement in the alpha-6T light absorption, roughness and the holes mobility. These findings participated in the significant enhancement of the PHJ-OPVs performances and their life time.

This research paper reports on spray pyrolysis deposited cerium dioxide (CeO2) thin films. Study consists of investigating the effect of Vanadium (V) doping on structural and optical characteristics of Ce1−xVxO2(0.02≤x≤0.06) layers using several characterization techniques. Indeed, X-ray diffraction patterns helped to estimate the crystallite size (D), micro-strain (ε), and dislocation density (δ). The crystallite size was found to decrease from 7 nm to 5 nm with the increase of V doping concentrations. The obtained dislocation density and micro-strain of the layers were found to be 1016 lines/m2 and 10−4 respectively. The micro-Raman results show the characteristic peak F2g of CeO2 at ~ 461 cm−1. The spectrum led to conclude that the peak intensity of the layers decreased in agreement with the increase in the V ratio. The atomic force micrograph showed a surface morphology transformation from spherical to flake upon doping. The surface roughness of the investigated thin layers was approximately 2-fold increased from 3.53 to 6.15 nm as a result of the increase in V doping proportions. The optical properties of the layers were studied in the wavelength range of 325–1000 nm and the overall transmittance of the layers was found to decrease with an increase in the V ratio. These results exhibit a slightly lower band-gap energy with the increase of V doping, from 3.19 eV to 3.08 eV. Optical parameters like refractive index (n), extinction coefficient (k), Urbach energy (Eu), optical conductivity (σ), and the real and imaginary part of dielectric constant (εr & εi) were estimated by using an UV-Visible spectrum.

The present work examines undoped and vanadium (V) doped cerium dioxide (CeO2) thin films prepared by an automated spray pyrolysis technique. The doping concentrations are 2,4, 6, and 8 at.%. Various characterization techniques were carried out to investigate the vanadium effect on the structural as well as the optical properties of the CeO2 films. The study also focused on inspecting the electrochemical characteristics of the CeO2 thin layers. The X-ray diffraction (XRD) results showed the presence of a polycrystalline cubic phase of the fluorite type of the CeO2 material, which is confirmed by results from Raman spectroscopy. The Scanning Electron Microscopy images showed that Vanadium doped films have excellent growth on the ITO substrate with a smooth surface. Optical analysis exhibits a decline in terms of the band gap value and the average transmittance within the visible range by increasing V doping proportions. Electrochemical properties were studied using cyclic voltammetry, which demonstrated that 4 at.% of V doped CeO2 thin films exhibited an excellent capacity to insert and extract the Li+ ions. The pure CeO2 film remained fully transparent after Li+insertion/disinsertion. These interesting results expand the field applications for this material, especially for electrochromic devices.

Silicene and germanene freestanding layers are usually described as a honeycomb lattice formed by two hexagonal sub-lattices presenting a height difference, namely the layer buckling. In this work, first-principles calculations show that silicene and germanene can be rippled at 0 K with various wavelengths, without any compressive strain of the layer. For germanene, the height difference between two Ge atoms from the same sub-lattice can be as high as 4.7 for an undulation length of 81 . The deformations are related to slight (lower than 1.7°) bond angle modifications, and the energy cost is remarkably low, lying between 0.1 and 0.8 meV per atom. These undulations modify the electronic structure, opening a gap of 15 meV.

Li and Sn codoped ZnO (LTZO) thin films have been successfully deposited on heated glass substrates at 450 degrees C using the spray pyrolysis technique, the effect of lithium of Sn-doped zinc oxide on the structural, morphological, optical and nonlinear optical properties was investigated using X-ray diffraction, transmission, the RMS average surface roughness, and third harmonic generation (THG). The value of optical band gap Eg was found to be decreased from 3.24 eV to 3.16 eV when the concentration of Li from 0 to 7%, while the concentration of Sn is fixed at 2%. The doping of ZnO films improves the nonlinear response and the highest susceptibility value chi((3)) = 13.422 x 10(-12) (esu) is found at concentration of lithium 7%.

Objective: Adalimumab has proven effective in psoriasis; however, secondary failure may result from the drug's immunogenicity. Prevalence data on the immunogenicity of biologicals, and of adalimumab in particular, are highly variable. We investigated the prevalence of anti-adalimumab antibodies and the association with clinical indexes and tumour necrosis factor alpha (TNF alpha) serum levels in psoriatic patients.Design: Case-control, longitudinal.Setting: Single centre.Participants: Patient groups: I (n=20) receiving biological therapies after switching from adalimumab; II (n=30) ongoing adalimumab therapy; III (n=30) novel adalimumab therapy; IV (n=15) biological therapies other than adalimumab.Healthy subjects: (group V; n=15) never treated with immunosuppressants or biologicals.Interventions: All groups were tested at enrolment. Group II was also tested at 12 months, and group III at 1, 3, and 6 months.Primary and secondary outcome measures: Standard clinical evaluations (Psoriasis Area Severity Index (PASI)), blood samples and two-site ELISA-based measurement of serum adalimumab trough levels, anti-adalimumab antibodies and TNF alpha.Results: The false-positive rate was 23% for adalimumab detection and 22% for anti-adalimumab antibodies in patients naive to adalimumab. Spurious positivity for anti-adalimumab antibodies (one-time-point positivity in group III during follow-up) accounted for 33% of the total. The prevalence of anti-drug antibodies was highest (87%) in group I patients. No correlations were found between the presence of anti-adalimumab antibodies or adalimumab levels and changes in PASI scores.Conclusions: High variability of results, high prevalence of false-positives and lack of association between anti-adalimumab antibodies and TNF alpha level/PASI score limit this assay's usefulness. Accurate clinical evaluation is key to early identification of treatment failures.

Fe2O3 and Fe2O3:Ca thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 500 °C to study their crystalline structure, composition and electrochemical properties as a function of Ca concentration (0, 2 at.%, 5 at.%, 10 at.%). The films were characterized by X-ray diffractometry (XRD), EDAX 9100 analyser and scanning electron microscopy (SEM). The cyclic voltammetry study showed that the 5 at.% Ca doped Fe2O3 thin films exhibit a good capacity to insert and extract the Li +

Li and Sn codoped ZnO (LTZO) thin films have been prepared by spray pyrolysis technique and their structural, morphological properties have been investigated. The films were characterized by Xray diffractometer (XRD), Scanning electron microscopy (SEM) and atomic force microcopy (AFM). XRD results revealed that all thin films (LTZO) are polycrystalline with à hexagonal wurtzite structure, the crystalline structures of the films showed depending on the increasing of lithium content. The (SEM) images showed that the LTZO thin films were changed with Li incorporation, the wrinkle structure disappeared with increasing Li content. It is remarqued that the surface is uniform with same clusters of irregularly shaped grain distributed at Li content at 7%. The AFM images of LTZO thin films decreased from 26.95 nm to 13.678 nm with the increase of Li concentration from 0% to 7% fixed Sn concentration of 2%.

The differences in systemic T-cell responses between patients with psoriatic arthritis (PsA) and patients with cutaneous psoriasis (Ps) are still largely unknown. To determine differential features that could be used to distinguish PsA from Ps, we compared the cytokine secretion profile of circulating T cells in patients with PsA, patients with cutaneous Ps and control subjects. We determined Th1, Th2 and Th17 cytokine secretion of anti-CD3-stimulated peripheral blood mononuclear cells (PBMCs) using a cytokine bead array. Normality of data distribution was assessed by the Shapiro-Wilk test, and statistical significance was calculated by the Mann-Whitney test. Phenotypic characterization of circulating T cells was performed by fluorescence-activated cell sorting analysis. We found that the major systemic differences distinguishing PsA from cutaneous Ps were the increased secretion of interleukin (IL)-2 by -CD3-stimulated PBMCs and a higher percentage of circulating CD3+ T cells expressing the proliferation marker CD71 in PsA. These results indicate IL-2 as a possible biomarker of PsA, and suggest a role of circulating T cells with high proliferative capacity in the pathogenesis of PsA.

Psoriasis is a chronic inflammatory skin disease affecting approximately 2% of the population. Important clinical benefits in the treatment of psoriasis have been obtained with TNF inhibitors, which have also contributed to the understanding of mechanisms involved in the disease pathogenesis. Despite the evidence that TNF-inhibitors block the inflammatory cascade and induce a decrease of Th17 responses in the psoriatic plaques, their primary mechanism of action in inhibiting the self-sustaining pathogenic cycle in psoriasis is not completely understood [1], [2], [3]. In this study we want to identify the early key events for the resolution of inflammation in psoriatic skin lesions upon treatment with TNF inhibitors. We used a translational approach combining quantitative gene expression analysis, clinical parameter of disease severity (PASI) and immunofluorescence analysis on tissue sections. Punch biopsies were collected from lesional skin at baseline and after 4 weeks of anti-TNF therapy (Etanercept, Infliximab or Adalimumab) and gene expression levels were evaluated by qRT-PCR performed by TaqMan Low Density Array (Human Immune Panel). The correlation between changes of gene expression in lesional skin and the decrease of PASI score after treatment was calculated with Spearman’s rank correlation test. Data were validated by immunofluorescence microscopy on skin biopsies collected at baseline and after anti-TNF therapy (4 weeks). We found that among genes down-modulated by TNF inhibitors, the ones that mostly associated with clinical remission were Ccr7, its ligand Ccl19 and dendritic cell maturation genes. Clinical remission was also associated with the decreased expression of T cell activation genes and Vegf. Importantly, the down-regulation of Ccr7 observed at 4 weeks also correlated with the clinical remission occurring at later time points. Immunofluorescence microscopy on skin biopsies showed that reduction of CCR7+ cells and CCL19 was paralleled by disaggregation of the dermal lymphoid-like tissue in the psoriatic plaque. These data show that early critical events for psoriasis resolution induced by TNF-blockade are the inhibition of CCR7/CCL19 axis and the disaggregation of the lymphoid-like tissue in the upper derma. This strongly supports the role of dermal lymphoid aggregate formation mediated by CCR7/CCL19 interaction in the pathogenesis of psoriasis.

Silicon substrates are often used to synthesize polycrystalline diamond films by microwave plasma assisted chemical vapour deposition technique (MPCVD). In the case of highly oriented diamond films, several steps are employed to carefully prepare the silicon surface (pre-treatment steps), to nucleate diamond crystals (nucleation step) and to thick the film (growth step). In this study, we characterize {100} silicon substrates and diamond released from its silicon substrate by electronic microscopies (TEM and SEM), by Atomic Force Microscopy (AFM) and by X-ray photoelectron spectroscopy (XPS), to follow the substrate transformations after each step, particularly the formation and the evolution of the silicon carbide and to characterise the diamond films grown on the carburised silicon. We show that according to the experimental conditions and the level of surface/gas contamination by carbon and silicon species, isolated islands or continuous β-SiC compound are formed over the silicon surface and can generate defects such as voids or strip structures that influence the subsequent diamond nucleation and growth.

Using complementary surface analysis techniques, we study the Ge growth on distinct SiC(0 0 0 1) reconstructions and elucidate complex mechanisms occurring by thermal activation. Two Si-rich reconstructions, (3 × 3) and , and one C-rich, , are concerned, on which Ge is found to grow in Stranski–Krastanov and Volmer–Weber modes, respectively. The best Ge-wetting layer is favoured on the (less Si-rich) because closest to a perfect truncated SiC(0 0 0 1) termination. At sufficiently high temperature, the Ge-wetting layer is organized in the form of a (4 × 4)Ge reconstruction for which we propose a first atomic model that is based on the 3 × 3 structure. Annealing Ge on the (3 × 3) and surfaces provokes spectacular successive 2D/3D and unusual 3D/2D transitions not only of Ge but also of Si and C, respectively, coming from the surface initial richness. In both cases, a phase separation is observed either in the 2D or 3D structures, which is unexpected for the Ge/Si binary system and somewhat usual for the Ge/C one. In the case of Ge on , a special 2D heterostructure graphite/Ge/SiC is achieved at the atomic level. This acts as a Schottky barrier and then can be promising for future possible applications.

The Ge growth behaviour on the 3x3 Si-rich surface termination of 4H-SiC(0001) has been investigated in this study. After the deposit of one Ge monolayer at room temperature by molecular beam epitaxy, the film is submitted to isochronal annealing cycles up to 1000°C. A phase separation between Si and Ge is observed during the annealing process accompanied by successive 2D/3D and unusual 3D/2D transitions for both elements. Si and Ge struggle for wetting the bare surface in order to minimize its surface energy. This behaviour seems also to be related to the strain difference induced by the misfit of Si (∼25%) and Ge (∼30%) with the 4H-SiC(0001) substrate.

Epitaxial Ge islands on a SiC(0001) substrate have been examined by reflection high-energy electron diffraction (RHEED). These islands have been obtained by depositing three monolayers of Ge at 500°C on a graphitized SiC (6√3×6√3)R30° reconstructed surface. This surface has been chosen for its ability to support epitaxial Ge island growth in a Volmer-Weber mode. The RHEED technique has allowed us to determine the epitaxy relationship and in-plane orientations between relaxed Ge and SiC(0001). Typical transmission electron diffraction patterns indicate that Ge grows according to only one epitaxy relationship Ge{111}||SiC(0001) that corresponds to two in-plane orientations, a preferential one Ge〈1¯1¯2〉||SiC〈11¯00〉 and a minority one Ge〈1¯1¯2〉||SiC〈101¯0〉 rotated by 30° around the growth 〈111〉-Ge (or [0001]-SiC) axis. Double spot RHEED patterns also point out a twinning for each in-plane orientation, a consequence of the three-fold order of the 〈111〉-Ge axis.