Novel Fluorescent Tetrahedral Zinc (II) Complexes Derived from 4-Phenyl-1-octyl-1H-imidazole Fused with Aryl-9H-Carbazole and Triarylamine Donor Units: Synthesis, Crystal Structures, and Photophysical Properties.

We present here the design, synthesis, and photophysical properties of two novel fluorescent zinc (II) complexes, ZnCl2(ImL1)2 and ZnCl2(ImL2)2, containing 4-(1-octyl-1H-imidazol-4-yl)-N,N-diphenyl-[1,1-biphenyl]-4-yl)-4-amine ImL1 and 9-(4-(1-octyl-1H-imidazol-4-yl)-[1,1-biphenyl]-4-yl)-9H-carbazole ImL2 ligands. The newly synthesized free ligands and their zinc (II) complexes were characterized using several spectroscopic techniques; their structures were identified by single-crystal X-ray diffraction; and their photophysical properties have been studied in the context of their chemical structure. The ZnCl2(ImL1)2 and ZnCl2(ImL2)2 complexes showed good thermal stability at 341 °C and 365 °C, respectively. Photophysical properties, including UV-Vis absorption spectra in ethanol solution and photoluminescence (PL) in both solid state and ethanol solution, were determined. UV-Vis adsorption data indicated that both free ligands had similar UV-Vis absorption properties, while their Zn (II) complexes had distinctive absorption characteristics. The fluorescence spectra show that both ligands and their corresponding Zn (II) complexes emit violet to cyan luminescence in the solid state at room temperature, while in ethanol solution at the same temperature, they exhibit efficient photoluminescence properties in the UV-A emission spectral region. Because of these photophysical properties, the synthesized ligands and their cognate Zn (II) complexes can be used as scaffolds for the potential development of optoelectronic materials.

Elucidating the Trajectory of the Charge Transfer Mechanism and Recombination Process of Hybrid Perovskite Solar Cells.

Perovskite-based solar cells (PSCs) have attracted attraction in the photovoltaic community since their inception in 2009. To optimize the performance of hybrid perovskite cells, a primary and crucial strategy is to unravel the dominant charge transport mechanisms and interfacial properties of the contact materials. This study focused on the charge transfer process and interfacial recombination within the n-i-p architecture of solar cell devices. The motivation for this paper was to investigate the impacts of recombination mechanisms that exist within the interface in order to quantify their effects on the cell performance and stability. To achieve our objectives, we firstly provided a rationale for the photoluminescence and UV-Vis measurements on perovskite thin film to allow for disentangling of different recombination pathways. Secondly, we used the ideality factor and impedance spectroscopy measurements to investigate the recombination mechanisms in the device. Our findings suggest that charge loss in PSCs is dependent mainly on the configuration of the cells and layer morphology, and hardly on the material preparation of the perovskite itself. This was deduced from individual analyses of the perovskite film and device, which suggest that major recombination most likely occur at the interface.

Tuning Magnetic Properties of a Carbon Nanotube-Lanthanide Hybrid Molecular Complex through Controlled Functionalization.

Molecular magnets attached to carbon nanotubes (CNT) are being studied as potential candidates for developing spintronic and quantum technologies. However, the functionalization routes used to develop these hybrid systems can drastically affect their respective physiochemical properties. Due to the complexity of this systems, little work has been directed at establishing the correlation between the degree of functionalization and the magnetic character. Here, we demonstrate the chemical functionalization degree associated with molecular magnet loading can be utilized for controlled tuning the magnetic properties of a CNT-lanthanide hybrid complex. CNT functionalization degree was evaluated by interpreting minor Raman phonon modes in relation to the controlled reaction conditions. These findings were exploited in attaching a rare-earth-based molecular magnet (Gd-DTPA) to the CNTs. Inductively coupled plasma mass spectrometry, time-of-flight secondary ion mass spectrometry and super conducting quantum interference device (SQUID) measurements were used to elucidate the variation of magnetic character across the samples. This controlled Gd-DTPA loading on the CNT surface has led to a significant change in the nanotube intrinsic diamagnetism, showing antiferromagnetic coupling with increase in the Weiss temperature with respect to increased loading. This indicates that synthesis of a highly correlated spin system for developing novel spintronic technologies can be realized through a carbon-based hybrid material.

Unravelling the interfacial interaction in mesoporous SiO2@nickel phyllosilicate/TiO2 core-shell nanostructures for photocatalytic activity.

Core-shell based nanostructures are attractive candidates for photocatalysis owing to their tunable physicochemical properties, their interfacial contact effects, and their efficacy in charge-carrier separation. This study reports, for the first time, on the synthesis of mesoporous silica@nickel phyllosilicate/titania (mSiO2@NiPS/TiO2) core-shell nanostructures. The TEM results showed that the mSiO2@NiPS composite has a core-shell nanostructure with a unique flake-like shell morphology. XPS analysis revealed the successful formation of 1:1 nickel phyllosilicate on the SiO2 surface. The addition of TiO2 to the mSiO2@NiPS yielded the mSiO2@NiPS/TiO2 composite. The bandgap energy of mSiO2@NiPS and of mSiO2@NiPS/TiO2 were estimated to be 2.05 and 2.68 eV, respectively, indicating the role of titania in tuning the optoelectronic properties of the SiO2@nickel phyllosilicate. As a proof of concept, the core-shell nanostructures were used as photocatalysts for the degradation of methyl violet dye and the degradation efficiencies were found to be 72% and 99% for the mSiO2@NiPS and the mSiO2@NiPS/TiO2 nanostructures, respectively. Furthermore, a recyclability test revealed good stability and recyclability of the mSiO2@NiPS/TiO2 photocatalyst with a degradation efficacy of 93% after three cycles. The porous flake-like morphology of the nickel phyllosilicate acted as a suitable support for the TiO2 nanoparticles. Further, a coating of TiO2 on the mSiO2@NiPS surface greatly affected the surface features and optoelectronic properties of the core-shell nanostructure and yielded superior photocatalytic properties.

Spectroscopic characterization and antimicrobial activity of nanoparticle doped cyclodextrin polyurethane bionanosponge.

This study reports on the spectroscopic characterization and antimicrobial potency of polyurethane cyclodextrin co-polymerized phosphorylated multiwalled carbon nanotube-doped Ag-TiO2 nanoparticle (pMWCNT-CD/Ag-TiO2) bionanosponge nanocomposite. The synthesis of pMWCNT-CD/Ag-TiO2 bionanosponge nanocomposite was carried out through the combined processes of amidation and polymerization reactions as well as the sol-gel method. The native nanosponge cyclodextrin and phosphorylated multiwalled carbon nanotube-nanosponge CD (pMWCNT-CD) polyurethanes were also prepared, and their antimicrobial activities carried out for comparison purposes. The synthesized bionanosponge polyurethane materials were characterized using Fourier-transform infrared (FTIR) spectroscopy, Laser Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) to give clear information regarding their structural, and dynamic physicochemical properties. The potency tests of the synthesized compounds were carried out against three bacterial strains Escherichia coli, Bacillus subtilis, Staphylococcus aureus, and two fungal representatives Aspergillus ochraceus and Aspergillus fumigatus, using the disc diffusion method. Micro dilution and agar plating were used to determine the minimum bactericidal concentration (MBC) and minimum fungicidal concentration (MFC), respectively. The results obtained revealed that pMWCNT-CD/Ag-TiO2 exhibits superior antibacterial and antifungal activities when compared to the other bionanosponge polymers tested. Thus, the bionanosponge polyurethane pMWCNT-CD/Ag-TiO2 nanocomposite can be considered as an active antimicrobial compound (AMC).

Annealing effect on the structural and optical behavior of ZnO:Eu3+ thin film grown using RF magnetron sputtering technique and application to dye sensitized solar cells.

Eu-doped ZnO (ZnO:Eu3+) thin films deposited by RF magnetron sputtering have been investigated to establish the effect of annealing on the red photoluminescence. PL spectra analysis reveal a correlation between the characteristics of the red photoluminescence and the annealing temperature, suggesting efficient energy transfer from the ZnO host to the Eu3+ ions as enhanced by the intrinsic defects levels. Five peaks corresponding to 5D0-7FJ transitions were observed and attributed to Eu3+ occupancy in the lattice sites of ZnO thin films. As a proof of concept a dye sensitized solar cell with ZnO:Eu3+ thin films of high optical transparency was fabricated and tested yielding a PCE of 1.33% compared to 1.19% obtained from dye sensitized solar cells (DSSC) with pristine ZnO without Eu produced indicating 11.1% efficiency enhancement which could be attributed to spectral conversion by the ZnO:Eu3+.

Effect of thermal treatment on ZnO:Tb3+ nano-crystalline thin films and application for spectral conversion in inverted organic solar cells.

Down conversion has been applied to minimize thermalization losses in photovoltaic devices. In this study, terbium-doped ZnO (ZnO:Tb3+) thin films were deposited on ITO-coated glass, quartz and silicon substrates using the RF magnetron sputtering technique fitted with a high-purity (99.99%) Tb3+-doped ZnO target (97% ZnO, 3% Tb) for use in organic solar cells as a bi-functional layer. A systematic study of the film crystallization dynamics was carried out through elevated temperature annealing in Ar ambient. The films were characterized using grazing incidence (XRD), Rutherford backscattering spectrometry (RBS), atomic force microscopy, and UV-visible transmittance and photoluminescence measurements at an excitation wavelength of 244 nm. The tunability of size and bandgap of ZnO:Tb3+ nanocrystals with annealing exhibited quantum confinement effects, which enabled the control of emission characteristics in ZnO:Tb3+. Energy transfer of ZnO → Tb3+ (5D3-7F5) was also observed from the photoluminescence (PL) spectra. At an inter-band resonance excitation of around 300-400 nm, a typical emission band from Tb3+ was obtained. The ZnO:Tb3+ materials grown on ITO-coated glass were then used as bi-functional layers in an organic solar cell based on P3HT:PCBM blend, serving as active layers in an inverted device structure. Energy transfer through down conversion between ZnO and Tb3+ led to enhanced absorption in P3HT:PCBM in the 300-400 nm range and subsequently augmented J sc of a Tb3+-based device by 17%.

Thinking strings: additional evidence for personal ornament use in the Middle Stone Age at Blombos Cave, South Africa.

Here we report on newly identified beads recovered from four Middle Stone Age levels at Blombos Cave and, in particular, on a cluster of 24 perforated Nassarius kraussianus shells that probably originate from a single beadwork. Contextual information, morphometric, technological and use-wear analysis of the 68 published beads and those recently found, coupled with experimental reproduction of wear patterns, allow us to reconstruct the most probable way in which the N. kraussianus shells were strung. The results reveal unexpected regularities but also variability through the various levels that we interpret as resulting from changes in beadwork manufacture and design over time. The Blombos Cave beads may document one of the first examples of changes in social norms affecting the production and design of symbolic material culture.

Formation of tungsten oxide nanostructures by laser pyrolysis: stars, fibres and spheres.

In this letter, the production of multi-phase WO3 and WO3-x (where x could vary between 0.1 and 0.3) nanostructures synthesized by CO2-laser pyrolysis technique at varying laser wavelengths (9.22-10.82 mm) and power densities (17-110 W/cm2) is reported. The average spherical particle sizes for the wavelength variation samples ranged between 113 and 560 nm, and the average spherical particle sizes for power density variation samples ranged between 108 and 205 nm. Synthesis of W18O49 (= WO2.72) stars by this method is reported for the first time at a power density and wavelength of 2.2 kW/cm2 and 10.6 µm, respectively. It was found that more concentrated starting precursors result in the growth of hierarchical structures such as stars, whereas dilute starting precursors result in the growth of simpler structures such as wires.