Origin of Enhancement of Orbital Magnetic Moment in SiO2-Coated Fe3O4 Nanocomposites Studied by X-ray Magnetic Circular Dichroism.

In this study, magnetic Fe3O4 nanoparticles (NPs) were dispersed uniformly by varying the thickness of the SiO2 coating, and their electronic and magnetic properties were investigated. X-ray diffraction confirmed the structural configuration of monophase inverse-spinel Fe3O4 NPs in nanometer size. Scanning electron microscopy revealed the formation of proper nonporous crystallite particles with a clear core-shell structure with silica on the surface of Fe3O4 NPs. The absorption mechanism studied through the zeta potential indicates that SiO2-coated Fe3O4 nanocomposites (SiO2@Fe3O4 NCs) possess electrostatic interactions to control their agglomeration in stabilizing suspensions by providing a protective shield of amorphous SiO2 on the oxide surface. High-resolution transmission electron microscopy images demonstrate a spherical morphology having an average grain diameter of ∼11-17 nm with increasing thickness of SiO2 coating with the addition of a quantitative presence and proportion of elements determined through elemental mapping and electron energy loss spectroscopy studies. Synchrotron-based element-specific soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) techniques have been involved in the bulk-sensitive total fluorescence yield mode to understand the origin of magnetization in SiO2@Fe3O4 NCs. The magnetization hysteresis of Fe3O4 was determined by XMCD. At room temperature, the magnetic coercivity (Hc) is as high as 1 T, which is about 2 times more than the value of the thin film and about 5 times more pronounced than that of NPs. For noninteracting single-domain NPs with the Hc spread from 1 to 3 T, the Stoner-Wohlfarth model provided an intriguing explanation for the hysteresis curve. These curves determine the different components of Fe oxides present in the samples that derive the remnant magnetization involved in each oxidation state of Fe and clarify which Fe component is responsible for the resultant magnetism and magnetocrystalline anisotropy based on noninteracting single-domain particles.

Gamma irradiation effect on photocatalytic properties of Cu and Sr ions codoped PbS.

Gamma-irradiation effects on photocatalytic action of PbS nanocrystallites codoped with Cu and Sr ions were performed for organic dye degradation. The physical and chemical characterizations of these nanocrystallites were examined employing X-ray diffraction, Raman, and field emission electron microscopic analysis. The optical bandgaps of gamma-irradiated PbS with co-dopants have shifted from 1.95 eV (pristine PbS) to 2.45 eV in the visible spectrum. Under direct sunlight, the photocatalytic action of these compounds against methylene blue (MB) was investigated. Observations indicated that gamma-irradiated Pb(0.98)Cu0.01Sr0.01S nanocrystallite sample exhibits a higher photocatalytic degradation activity of 74.02% in 160 min and stability of 69.4% after three cycles, suggesting that gamma irradiation could potentially influence organic MB degradation. This is due to combined action of high-energy gamma irradiation (at an optimzed dose), which causes sulphur vacancies, and defects created by dopant ions, which alter the crystal structure by inducing strain in the crystal lattice, hence altering the crystallinity of PbS.

Thermoelectric and Photovoltaic Properties of Mn-Doped Kesterite Cu2Zn1-xMnxSnSe4.

The semiconductor Cu2ZnSnSe4 (CZTSe) is a promising candidate for both thermoelectric and photovoltaic energy harvesting applications due to a combination of features such as direct band gap, high absorption coefficient, and low thermal conductivity. We report the solid-state synthesis and characterization of Mn-doped Cu2Zn1-xMnxSnSe4 (x = 0, 0.05, 0.10, and 0.15) in an attempt to explore the effect of isovalent substitution at the Zn site. X-ray diffraction and Raman spectroscopy of all specimens confirmed the formation of a single-phase tetragonal kesterite structure (space group I4̅). The band gap obtained by UV-visible diffuse reflectance measurements was 1.42 eV for all compositions. Thermoelectric properties were measured in the range 300-785 K. Electrical resistivity was metallic and reduced on Mn doping, while the Seebeck coefficient exhibited a p-type semiconducting behavior that enhanced on Mn doping, with associated enhancement of the power factor. Lattice thermal conductivity showed a 1/T behavior, falling from about 1.9-2.7 W m-1 K-1 at 300 K to 0.51-0.9 W m-1 K-1 above 750 K. The combined effect of enhanced power factor and reduced lattice thermal conductivity resulted in a figure of merit ZT in the range of 0.19-0.42 above 750 K. Thin-film photovoltaic devices with a CZTSe absorber and an SnSe electron transport layer gave 3.2% efficiency.

Photo generated charge transport studies of defects-induced shuttlecock-shaped ZnO/Ag hybrid nanostructures.

We report the stimulating effects of interfacial charge transfer process between spherical Ag nanoparticles and shuttlecock-shaped ZnO nanostructures observed by UV-visible spectroscopy and x-ray absorption spectroscopy. In specific, ZnO nanorods and shuttlecock-shaped ZnO/Ag nanostructures were developed using a simple chemical colloidal method and characterized for structural variations using XRD. The observed red shift in plasmonic peak and the increase in Urbach energy signify interfacial interactions and increased randomness in the hybrid ZnO/Ag nanostructures. Simultaneously, the enhanced intensity of deep-level emission in the ZnO/Ag hybrid suggests the increased recombination rate of electron-hole pairs. The red and blue emissions evolving with temperature subsequently suggests the presence of oxygen vacancies or zinc interstitials in the system. The decrease in intensities and emerging features in O K-edge and Zn L-edge indicates the charge transfer from Ag to ZnO at the interface of ZnO/Ag hybrids. Moreover, the differences in absorption edges with alternating light on/off conditions were analyzed for the exploitation of this ZnO-based system in various applications.

Synchrotron-based VUV excitation-induced ultrahigh quality cool white light luminescence from Sm-doped ZnO.

We report that the rare-earth (RE) ion, Sm-doped ZnO, acts as white light emitting vacuum ultraviolet (VUV) phosphors and possesses an ultrahigh color rendering index (CRI) and color quality scale (CQS). The VUV-excited emission spectra measured from the synchrotron source reveal the emergence of multi-color emission bands in the visible-IR region and substantially depend on the concentration of Sm3+ ions. A mechanism is proposed to elucidate the origin behind the high-energy bandgap excitation of the host charge carrier and subsequent energy transfer to the Sm3+ states leading to additional green-yellow-orange emission bands of Sm3+(4G5/2→6HJ(J=5/2,7/2,and9/2)). High-quality cool white light (correlated color temperature 5600 K) having CIE coordinates (0.33, 0.35) with a CRI as high as 95.89 and a CQS value of 94.49 is achieved for Zn0.985Sm0.015O under synchrotron VUV radiations. This Letter demonstrates that RE activated ZnO-based phosphors are expected to be a promising candidate in solid state lighting, as well as plasma display devices.

γ-Ray-Induced Photocatalytic Activity of Bi-Doped PbS toward Organic Dye Removal under Sunlight.

Photocatalysts based on semiconducting chalcogenides due to their adaptable physio-chemical characteristics are attracting attention. In this work, Bi-doped PbS (henceforth PbS:Bi) was prepared using a straightforward chemical precipitation approach, and the influence of γ-irradiation on PbS's photocatalytic ability was investigated. Synthesized samples were confirmed structurally and chemically. Pb(1-x)BixS (x = 0, 0.005, 0.01, 0.02) samples that were exposed to gamma rays showed fine-tuning of the optical bandgap for better photocatalytic action beneath visible light. The photocatalytic degradation rate of the irradiated Pb0.995Bi0.005S sample was found to be 1.16 times above that of pure PbS. This is due to the occupancy of Bi3+ ions at surface lattice sites as a result of their lower concentration in PbS, which effectively increases interface electron transport and the annealing impact of gamma irradiation. Scavenger tests show that holes are active species responsible for deterioration of the methylene blue. The irradiated PbS:Bi demonstrated high stability after being used repeatedly for photocatalytic degradation.

Novel GdTaO4 phase for efficient photocatalytic degradation of organic dye under visible light irradiation: An X-ray spectroscopic investigation.

The novel GdTaO4 phase exhibits good photocatalytic activity under visible light irradiation and holds great promise for the removal of organic dyes from industrial wastes. The GdTaO4 samples were synthesized using the hydrothermal and calcination process with different weight ratios of gadolinium nitrate hydrate (G) and tantalum pentachloride (T), and their structural studies confirmed the formation of the GdTaO4 (GT) phase. Among the samples, GT-4 (with a weight ratio of 4:1) exhibited the highest photocatalytic activity for the degradation of Methyl Orange (MO) dye under visible light irradiation. To enhance the photocatalytic performance, H2O2 was used as a green additive, and the photocatalytic abilities were examined by varying dye types and concentrations. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) revealed the local atomic and electronic structures around Ta and Gd and highlighted the contribution of Gd3+ to the GT system, which is a crucial factor in supporting the enhanced photocatalytic performance. Moreover, in-situ XAS at Gd M5-edge and O K-edge were examined under illumination/dark conditions to explore the electronic structures of photo-excited electron transition in the photocatalytic process. The analytical results provided strong evidence correlating the electronic structure and photocatalytic property of the GT. This study demonstrates that GdTaO4 exhibits good photocatalytic activity under visible light irradiation, making it a promising new Ta-based photocatalyst for the effective removal of organic dyes from industrial wastes.

Swift Heavy Ion-Induced Reactivity and Surface Modifications in Indium Thin Films.

As an energetic ion traverses a target material, it loses its energy through the processes of electronic energy loss (S e) and nuclear energy loss (S n). Controlled swift heavy ion (SHI) irradiation on solid targets produces its effects through both of these mechanisms, as a consequence of which modifications occur in the structure, surface morphology, and magnetic and optical properties, apart from ion implantation and ion-induced reactivity. A systematic investigation of these effects can be useful in developing standard protocols for creating desired effects in materials using specific ion beams. In this study, indium films of thickness 25 nm were deposited on silicon substrates and were subjected to 100 MeV O7+ and 100 MeV Si7+ ion irradiation, with the fluences varying from 1 × 1011 to 1 × 1013 ions/cm2. The pristine and SHI-irradiated films were then characterized using glancing incidence X-ray diffraction (GIXRD), Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The motive was to identify the effects of irradiation with different ion species having large variations in electronic and nuclear energy losses. While the RBS results suggest that sputtering is extremely low and that there are no major changes in the film composition due to ion beam-induced mixing, the GIXRD analysis indicates that increasing the ion fluence reduces the crystallinity of the film for both the ions. Ion beam irradiation with O7+ ions, however, results in beam-induced reactivity, as the GIXRD scan shows characteristic peaks from indium oxide (In2O3), which become the predominant peaks at the highest fluence used here. Si7+ ion irradiation results in a narrowing of the particle size distribution on the surface, with no evidence of reactivity. SEM results indicate fusion and fragmentation of grains with the increase in the ion fluences, and AFM images reveal an increase in the surface roughness of a few percent when irradiated with both 100 MeV O7+ and 100 MeV Si7+ ions.

Visible light-assisted degradation of 4-nitrophenol and methylene blue using low energy carbon ion-implanted ZnO nanorod arrays: Effect on mechanistic insights and stability.

The present investigation demonstrates an enhancement of the visible photocatalytic activities by C ion implantation in ZnO nanorod arrays (NRAs). Vertically aligned ZnO NRAs were prepared by seed layer assisted solution-phase growth and implanted with 70 keV carbon ions at various fluencies: 1E15, 5E15, 1E16, and 3E16 ions/cm2. X-ray diffraction and FESEM results revealed the crystalline 1D ZnO NRAs having a length of ∼3 µm with a diameter in the range of 150-200 nm. C implantation induces the absorption towards the visible region and a substantial decrease in the optical bandgap energy from 3.2 eV to 2.43 eV. The photocatalytic activities (PC) of C ion-implanted ZnO NRAs were investigated through the degradation of 4-Nitrophenol (4-NP) and methylene blue dye (MB) under ambient visible light irradiation. The degradation efficiency of C ion-implanted ZnO NRAs increases compared to the pristine ZnO NRAs from 60.12% to 93.7% and 48.6 to 97.5% for MB and 4-NP, respectively. The synergistic effects of low energy carbon ion-induced bulk and surface interface electronic states facilitate a narrow band of visible light absorption and efficient charge separation to increase the visible-light-driven photocatalytic performance of ZnO NRAs.

Effects of Heavy Ion Irradiation on the Thermoelectric Properties of In2(Te1-xSex)3 Thin Films.

Ion irradiation is an exceptionally effective approach to induce controlled surface modification/defects in semiconducting thin films. In this investigation, ion-irradiated Se-Te-based compounds exhibit electrical transport properties that greatly favor the transformation of waste heat into electricity. Enhancements of both the Seebeck coefficient (S) and the power factor (PF) of In2(Te0.98Se0.02)3 films under 120 MeV Ni9+ ion irradiation were examined. The maximum S value of the pristine film was about ~221 µVK-1. A significantly higher S value of about ~427 µVK-1 was obtained following irradiation at 1 × 1013 ions/cm2. The observed S values suggest the n-type conductivity of these films, in agreement with Hall measurements. Additionally, Ni ion irradiation increased the PF from ~1.23 to 4.91 µW/K2m, demonstrating that the irradiated films outperformed the pristine samples. This enhancement in the TE performance of the In2(Te0.98Se0.02)3 system is elucidated by irradiation-induced effects that are revealed by structural and morphological studies.

Laser Transmission Welding of Semi-Crystalline Polymers and Their Composites: A Critical Review.

The present review provides an overview of the current status and future perspectives of one of the smart manufacturing techniques of Industry 4.0, laser transmission welding (LTW) of semi-crystalline (SC) polymers and their composites. It is one of the most versatile techniques used to join polymeric components with varying thickness and configuration using a laser source. This article focuses on various parameters and phenomena such as inter-diffusion and microstructural changes that occur due to the laser interaction with SC polymers (specifically polypropylene). The effect of carbon black (size, shape, structure, thermal conductivity, dispersion, distribution, etc.) in the laser absorptive part and nucleating agent in the laser transmissive part and its processing conditions impacting the weld strength is discussed in detail. Among the laser parameters, laser power, scanning speed and clamping pressure are considered to be the most critical. This review also highlights innovative ideas such as incorporating metal as an absorber in the laser absorptive part, hybrid carbon black, dual clamping device, and an increasing number of scans and patterns. Finally, there is presented an overview of the essential characterisation techniques that help to determine the weld quality. This review demonstrates that LTW has excellent potential in polymer joining applications and the challenges including the cost-effectiveness, innovative ideas to provide state-of-the-art design and fabrication of complex products in a wide range of applications. This work will be of keen interest to other researchers and practitioners who are involved in the welding of polymers.

Medium Energy Carbon and Nitrogen Ion Beam Induced Modifications in Charge Transport, Structural and Optical Properties of Ni/Pd/n-GaN Schottky Barrier Diodes.

The irradiation effects of carbon and nitrogen medium energy ions (MEI) on charge transport, structural and optical properties of Ni/Pd/n-GaN Schottky barrier diodes are reported. The devices are exposed to 600 keV C2+ and 650 keV N2+ ions in the fluence range of 1 × 1013 to 1 × 1015 ions cm-2. The SRIM/TRIM simulations provide quantitative estimations of damage created along the trajectories of ion beams in the device profile. The electrical parameters like Schottky barrier height, series resistance of the Ni/Pd/n-GaN Schottky barrier diodes decreases for a fluence of 1 × 1013 ions cm-2 and thereafter increases with an increase in fluence of 600 keV C2+ and 650 keV N2+ ions. The charge transport mechanism is influenced by various current transport mechanisms along with thermionic emission. Photoluminescence studies have demonstrated the presence of yellow luminescence in the pristine samples. It disappears at higher fluences due to the possible occupancy of Ga vacancies. The presence of the green luminescence band may be attributed to the dislocation caused by the combination of gallium vacancy clusters and impurities due to MEI irradiation. Furthermore, X-ray diffraction studies reveal that there is a decrease in the intensity and shift in the diffraction peaks towards the lower side of two thetas. The reductions in the intensity of C2+ ion irradiation is more when compared to N2+ ion irradiation, which may be attributed to change in the mean atomic scattering factor on a given site for light C2+ ion as compared to N2+ ion.

Nitrogen-Implanted ZnO Nanorod Arrays for Visible Light Photocatalytic Degradation of a Pharmaceutical Drug Acetaminophen.

The present study focuses on the effects of nitrogen (N) ion implantation in vertically aligned ZnO nanorod arrays (NRAs) and the photocatalytic degradation of acetaminophen. The X-ray diffraction of these NRAs exhibit a wurtzite structure with a predominant (002) diffraction peak that shifts slightly after N-ion implantation. The field emission scanning electron microscopic images of as-prepared NRAs show a length of ∼4 µm and diameter of ∼150 nm. UV-visible spectroscopy reveals that the band gap of pristine ZnO NRAs decreases from 3.2 to 2.18 eV after N-ion implantation. Under visible irradiation, the N-ion-implanted ZnO catalyst exhibits significant enhancement of the photocatalytic degradation of acetaminophen from 60.0 to 98.46% for 120 min.

Tuning the Electrical and Thermoelectric Properties of N Ion Implanted SrTiO3 Thin Films and Their Conduction Mechanisms.

The SrTiO3 thin films were fabricated by pulsed laser deposition. Subsequently ion implantation with 60 keV N ions at two different fluences 1 × 1016 and 5 × 1016 ions/cm2 and followed by annealing was carried out. Thin films were then characterized for electronic structure, morphology and transport properties. X-ray absorption spectroscopy reveals the local distortion of TiO6 octahedra and introduction of oxygen vacancies due to N implantation. The electrical and thermoelectric properties of these films were measured as a function of temperature to understand the conduction and scattering mechanisms. It is observed that the electrical conductivity and Seebeck coefficient (S) of these films are significantly enhanced for higher N ion fluence. The temperature dependent electrical resistivity has been analysed in the temperature range of 80-400 K, using various conduction mechanisms and fitted with band conduction, near neighbour hopping (NNH) and variable range hopping (VRH) models. It is revealed that the band conduction mechanism dominates at high temperature regime and in low temperature regime, there is a crossover between NNH and VRH. The S has been analysed using the relaxation time approximation model and dispersive transport mechanism in the temperature range of 300-400 K. Due to improvement in electrical conductivity and thermopower, the power factor is enhanced to 15 µWm-1 K-2 at 400 K at the higher ion fluence which is in the order of ten times higher as compared to the pristine films. This study suggests that ion beam can be used as an effective technique to selectively alter the electrical transport properties of oxide thermoelectric materials.

Controlling room temperature ferromagnetism and band gap in ZnO nanostructured thin films by varying angle of implantation.

The defects in the host lattice play a major role in tuning the surface roughness, optical band gap and the room temperature ferromagnetism (RTFM) of ZnO thin films. Herein, we report a novel approach to tailor the band gap and RTFM of a ZnO nanostructure by varying the angle of implantation of 60 keV N ions keeping the ion fluence of 1 × 1016 ions per cm2 and the beam size of 3 mm constant. The implantation was performed by changing the thin films' orientations at 30°, 60° and 90° with respect to the incident beams. Remarkably, an enhancement of ∼6 times in RTFM, tuning in band gap from 3.27 to 3.21 eV and ∼60% reduction in surface roughness were noticed when the ion implantation was done at 60° to the normal. This novel technique may be suitable for tuning the physical properties of nanostructures for their application in the spintronics, semiconductor and solar cell industries.