Photocatalytic Activity of N-Doped ZrO2 Thin Films Determined by Direct and Indirect Irradiation.

In this paper, we investigate the decomposition of a toxic organic compound, Rhodamine B, by the photocatalytic activities of undoped and nitrogen-doped ZrO2 thin films, deposited using the HiPIMS technique. The investigation was performed in the presence and in the absence of H2O2, for two types of experimental arrangements: the irradiation of the films, followed by dipping them in the Rhodamine B solutions, and the irradiation of the films dipped in the solution. The two situations were named "direct irradiation" and "indirect irradiation", respectively. Methods like XRD, AFM, XPS, DRS, water/film surface contact angle, and spectrophotometry were used to obtain information on the films' structure, surface morphology, elemental composition of the films surface, optical band gap, hydrophilicity, and photocatalytic activity, respectively. All these properties were described and correlated. By N-doping ZrO2, the films become absorbent in the visible domain, so that the solar light could be efficiently used; the films' hydrophilic properties improve, which is an important fact in self-cleaning applications; and the films' photocatalytic activity for the decomposition of Rhodamine B becomes better. The addition of hydrogen peroxide acted as an inhibitor for all systems and not as an accelerator of the photocatalytic reactions as expected.

Study of Tunable Dielectric Permittivity of PBDB-T-2CL Polymer in Ternary Organic Blend Thin Films Using Spectroscopic Ellipsometry.

The ellipsometric analyses reported in this paper present a novelty by bringing an in-depth optical investigation of some ternary organic blends. This study focuses on the tunability and control of the relative permittivity of active layers by varying the weight ratio of blended materials spin-coated as thin films. To investigate this, an extensive approach based on spectroscopic ellipsometry was conducted on ternary blend (D:A1:A2) thin films, involving a donor [D = chlorinated conjugated polymer (PBDB-T-2Cl)] and two acceptor materials [A1 = a non-fullerene (ITIC-F) and A2 = a fullerene (PCBM)]. The refractive index constitutes a key parameter that exposes insights into the feasibility of photovoltaic cells by predicting the trajectory of light as it transits the device. In this term, higher obtained refractive indexes support higher absorption coefficients. Notably, the dielectric constant can be rigorously tuned and finely calibrated by modest variations in the quantity of the third element, resulting in considerable modifications. Moreover, the inclusion of fullerene in blends, as the third element, results in a smooth topographical profile, further refining the surface of the film. From an electrical point of view, the ternary blends outperform the polymer thin films. The synergistic interaction of constituents emphasizes their potential to enhance solar conversion devices.

Band-gap engineering of zirconia by nitrogen doping in reactive HiPIMS: a step forward in developing innovative technologies for photocatalysts synthesis.

In the global context of climate change and carbon neutrality, this work proposes a strategy to improve the light absorption of photocatalytic water-splitting materials into the visible spectrum by anion doping. In this framework, reactive high power impulse magnetron sputtering (HiPIMS) of a pure Zr target in Ar/N2/O2 gas mixture was used for the deposition of crystalline zirconium oxynitride (ZrO2-xNx) thin films with variable nitrogen doping concentration and energy band-gap. The nitrogen content into these films was controlled by the discharge pulsing frequency, which controls the target surface poisoning and peak discharge current. The role of the nitrogen doping on the optical, structural, and photocatalytic properties of ZrO2-xNx films was investigated. UV-Vis-NIR spectroscopy was employed to investigate the optical properties and to assess the energy band-gap. Surface chemical analysis was performed using X-ray photoelectron spectroscopy, while structural analysis was carried out by X-ray diffraction. The increase in the pulse repetition frequency determined a build-up in the nitrogen content of the deposited ZrO2-xNx thin films from ∼10 to ∼25 at.%. This leads to a narrowing of the optical band-gap energy from 3.43 to 2.20 eV and endorses efficient absorption of visible light. Owing to its narrow bandgap, ZrO2-xNx thin films obtained by reactive HiPIMS can be used as visible light-driven photocatalyst. For the selected processing conditions (pulsing configuration and gas composition), it was found that reactive HiPIMS can suppress the hysteresis effect for a wide range of frequencies, leading to a stable deposition process with a smooth transition from compound to metal-sputtering mode.

Optical and Structural Analysis of TiO2-SiO2 Nanocomposite Thin Films Fabricated via Pulsed Laser Deposition Technique.

TiO2-SiO2 nanocomposite thin films have gained the attention of the scientific community due to their unique physical and chemical properties. In this paper, we report on the fabrication and characterization of a TiO2-SiO2 nanocomposite disk-shaped target. The target was used for the deposition of TiO2-SiO2 nanocomposite thin films on fluorine-doped tin oxide/glass substrates using the pulsed laser deposition (PLD) technique. The thicknesses of the thin films were fixed to 100 nm, and the deposition temperature ranged from room temperature to 300 °C. As revealed by the microstructural and morphological characterizations revealed, the TiO2-SiO2 nanocomposite thin films are amorphous and display homogeneous distribution. The determined values of the indirect optical band gap range from 2.92 to 3.07 eV, while those of the direct optical band gap lie between 3.50 and 3.55 eV. Additionally, as the deposition temperature decreases, the light transmission increases in the visible and in the ultraviolet ranges, which is suitable for flexible perovskite solar cells. This research can uncover new insights into the fabrication of amorphous TiO2-SiO2-based nanostructured thin films using the PLD technique for perovskite solar cell technology.

On the Deposition Process of Ceramic Layer Thin Films for Low-Carbon Steel Pipe Protection.

Ceramic thin films with variable thicknesses have been used in many applications. In order to protect the petroleum transportation pipes against the harmful H2S action, two ceramic materials as thin layers are proposed. In this article, pulsed laser deposition (PLD) of ceramic layers by in situ time-resolved optical techniques is investigated. Two ceramic materials were used as targets and real-time monitoring of the PLD process was realized via ICCD fast camera imaging and optical emission spectroscopy. The space-time displacement of the ceramic emissions was analyzed in order to determine the plasma structure and respective kinetic energies. Spectral-resolved investigation allowed the determination of plasma species individual velocities (in the first case: 43 km/s for C ionic species, 11 km/s for Si, from 25 to 5 km/s for atomic species; in the second case: 32 km/s for C ionic species, 11 km/s for W species, and 15 and 53 km/s for neutral species). SEM and AFM techniques were implemented to analyze the resulting ceramic layers showing homogeneous surfaces with characteristic material droplets. The ablation crater also reveals selective ablation during the deposition process. EDX results show that Al/Si is retained in the thin films similar to the target composition.

Efficient Removal of Methylene Blue and Ciprofloxacin from Aqueous Solution Using Flower-like, Nanostructured ZnO Coating under UV Irradiation.

Flower-like ZnO architectures assembled with many nanorods were successfully synthesized through Thermionic Vacuum Arc, operated both in direct current (DC-TVA) and a pulsed mode (PTVA), and coupled with annealing in an oxygen atmosphere. The prepared coatings were analysed by scanning-electron microscopy with energy-dispersive X-ray-spectroscopy (SEM-EDX), X-ray-diffraction (XRD), and photoluminescence (PL) measurements. By simply modifying the TVA operation mode, the morphology and uniformity of ZnO nanorods can be tuned. The photocatalytic performance of synthesized nanostructured ZnO coatings was measured by the degradation of methylene-blue (MB) dye and ciprofloxacin (Cipro) antibiotic. The ZnO (PTVA) showed enhancing results regarding the photodegradation of target contaminants. About 96% of MB molecules were removed within 60 min of UV irradiation, with a rate constant of 0.058 min-1, which is almost nine times higher than the value of ZnO (DC-TVA). As well, ZnO (PTVA) presented superior photocatalytic activity towards the decomposition of Cipro, after 240 min of irradiation, yielding 96% degradation efficiency. Moreover, the agar-well diffusion assay performance against both Gram-positive and Gram-negative bacteria confirms the degradation of antibiotic molecules by the UV/ZnO (PTVA) approach, without the formation of secondary hazardous products during the photocatalysis process. Repeated cyclic usage of coatings revealed excellent reusability and operational stability.

High-Power Laser Deposition of Chitosan Polymers: Medical and Environmental Applications.

High-power laser irradiation interaction with natural polymers in biocomposites and Laser-Induced Chitin Deacetylation (LICD) was studied in this work, in order to produce thin films consisting of chitosan composite. The new method can lead to a cutting-edge technology, as a response to the concern regarding the accumulation of "natural biological waste" and its use. The process consists of high-power laser irradiation applied on oyster shells as the target and deposition of the ablated material on different substrates. The obtained thin films we analyzed by FTIR, UV-VIS and LIF spectroscopy, as well as SEM-EDS and AFM. All the results indicated that chitin was extracted from the shell composite material and converted to chitosan by deacetylation. It was, thus, evidenced that chemical transformation in the chitin polymer side-chain occurs during laser irradiation of the oyster shell and in the resulted plasma plume of ablation. The numerical simulation in COMSOL performed for this study anticipates and confirms the experimental results of chitin deacetylation, also providing information about the conditions required for the physico-chemical processes involved. The high sorption properties of the thin films obtained by a LICD procedure is evidenced in the study. This quality suggests that they should be used in transdermal patch construction due to the known hemostatic and antibacterial effects of chitosan. The resulting composite materials, consisting of the chitosan thin films deposited on hemp fabric, are also suitable for micro-filters in water decontamination or in other filtering processes.

Room Temperature Deposition of Nanocrystalline SiC Thin Films by DCMS/HiPIMS Co-Sputtering Technique.

Due to an attractive combination of chemical and physical properties, silicon carbide (SiC) thin films are excellent candidates for coatings to be used in harsh environment applications or as protective coatings in heat exchanger applications. This work reports the deposition of near-stoichiometric and nanocrystalline SiC thin films, at room temperature, on silicon (100) substrates using a DCMS/HiPIMS co-sputtering technique (DCMS-direct current magnetron sputtering; HiPIMS-high-power impulse magnetron sputtering). Their structural and mechanical properties were analyzed as a function of the process gas pressure. The correlation between the films' microstructure and their mechanical properties was thoroughly investigated. The microstructure and morphology of these films were examined by appropriate microscopic and spectroscopic methods: atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Raman spectroscopy, while their mechanical and tribological properties were evaluated by instrumented indentation and micro-scratch techniques. The lowest value of the working gas pressure resulted in SiC films of high crystallinity, as well as in an improvement in their mechanical performances. Both hardness (H) and Young's modulus (E) values were observed to be significantly influenced by the sputtering gas pressure. Decreasing the gas pressure from 2.0 to 0.5 Pa led to an increase in H and E values from 8.2 to 20.7 GPa and from 106.3 to 240.0 GPa, respectively. Both the H/E ratio and critical adhesion load values follow the same trend and increase from 0.077 to 0.086 and from 1.55 to 3.85 N, respectively.

Sequential Synthesis Methodology Yielding Well-Defined Porous 75%SrTiO3/25%NiFe2O4 Nanocomposite.

In this research, we reported on the formation of highly porous foam SrTiO3/NiFe2O4 (100-xSTO/xNFO) heterostructure by joint solid-state and sol-gel auto-combustion techniques. The colloidal assembly process is discussed based on the weight ratio x (x = 0, 25, 50, 75, and 100 wt %) of NiFe2O4 in the 100-xSTO/xNFO system. We proposed a mechanism describing the highly porous framework formation involving the self-assembly of SrTiO3 due to the gelation process of the nickel ferrite. We used a series of spectrophotometric techniques, including powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N2 adsorption isotherms method, UV-visible diffuse reflectance spectra (UV-Vis DRS), vibrating sample magnetometer (VSM), and dielectric measurements, to investigate the structural, morphological, optical, magnetic, and dielectric properties of the synthesized samples. As revealed by FE-SEM analysis and textural characteristics, SrTiO3-NiFe2O4 nanocomposite self-assembled into a porous foam with an internally well-defined porous structure. HRTEM characterization certifies the distinctive crystalline phases obtained and reveals that SrTiO3 and NiFe2O4 nanoparticles were closely connected. The specific magnetization, coercivity, and permittivity values are higher in the 75STO/25NFO heterostructure and do not decrease proportionally to the amount of non-magnetic SrTiO3 present in the composition of samples.

Ge-Sb-Te Chalcogenide Thin Films Deposited by Nanosecond, Picosecond, and Femtosecond Laser Ablation.

Ge-Sb-Te thin films were obtained by ns-, ps-, and fs-pulsed laser deposition (PLD) in various experimental conditions. The thickness of the samples was influenced by the Nd-YAG laser wavelength, fluence, target-to-substrate distance, and deposition time. The topography and chemical analysis results showed that the films deposited by ns-PLD revealed droplets on the surface together with a decreased Te concentration and Sb over-stoichiometry. Thin films with improved surface roughness and chemical compositions close to nominal values were deposited by ps- and fs-PLD. The X-ray diffraction and Raman spectroscopy results showed that the samples obtained with ns pulses were partially crystallized while the lower fluences used in ps- and fs-PLD led to amorphous depositions. The optical parameters of the ns-PLD samples were correlated to their structural properties.