Investigating the Effect of Steric Hindrance within CdS Single-Source Precursors on the Material Properties of AACVD and Spin-Coat-Deposited CdS Thin Films.

Cadmium sulfide (CdS) is an important semiconductor for electronic and photovoltaic applications, particularly when utilized as a thin film for window layers in CdTe solar cells. Deposition of thin-film CdS through the decomposition of single-source precursors is an attractive approach due to the facile, low-temperature, and rapid nature of this approach. Tailoring the precursor to affect the decomposition properties is commonly employed to tune desirable temperatures of decomposition. However, altering the precursor structure and the effect this has on the nature of the deposited material is an area far less commonly investigated. Here, we seek to investigate this by altering the ligands around the Cd metal center to increase the steric hindrance of the precursor and investigate the effect this has on the decomposition properties and the properties of deposited thin-film CdS from these precursors. For this, we report the synthesis of four CdS precursors with xanthate and pyridyl ligands ([Cd(n-ethyl xanthate)2(3-methyl pyridine)2] [1], [Cd(n-ethyl xanthate)2(3,5-lutidine)2] [2], [(Cd2(isopropyl xanthate)4(3-methyl pyridine)2)n] [3], and [Cd(isopropyl xanthate)2(3,5-lutidine)2] [4]). These single-source precursors for CdS were fully characterized by elemental analysis, NMR spectroscopy, single-crystal X-ray diffraction (XRD), and thermogravimetric analysis. It was found that even with subtle alterations in the xanthate (n-ethyl to isopropyl) and pyridine (3-methyl and 3,5-dimethyl) ligands, a range of hexa-coordinate precursors were formed (two with cis configuration, one with trans configuration, and one as a one-dimensional (1D) polymer). These four precursors were then used in aerosol-assisted chemical vapor deposition (AACVD) and spin-coating experiments to deposit eight thin films of CdS, which were characterized by Raman spectroscopy, powder X-ray diffraction, and scanning electron microscopy. Comparative quantitative information concerning film thickness and surface roughness was also determined by atomic force microscopy. Finally, the optical properties of all thin films were characterized by ultraviolet-visible (UV-Vis) absorption spectroscopy, from which the band gap of each deposited film was determined to be commensurate with that of bulk CdS (ca. 2.4 eV).

Synthesis of High Entropy Lanthanide Oxysulfides via the Thermolysis of a Molecular Precursor Cocktail.

High entropy (HE) materials have received significant attention in recent years, due to their intrinsically high levels of configurational entropy. While there has been significant work exploring HE alloys and oxides, new families of HE materials are still being revealed. In this work we present the synthesis of a novel family of HE materials based on lanthanide oxysulfides. Here, we implement lanthanide dithiocarbamates as versatile precursors that can be mixed at the molecular scale prior to thermolysis in order to produce the high entropy oxysulfide. The target of our synthesis is the HE Ln2SO2 phase, where Ln = Pr, Nd, Gd, Dy, Er and where Ln = Pr, Nd, Gd, Dy for 5 and 4 lanthanide samples, respectively. We confirmed the structure of samples produced by powder X-ray diffraction, electron microscopy, and high-resolution energy dispersive X-ray spectroscopy. Optical spectroscopy shows a broad emission feature centered around 450 nm as well as a peak in absorption at around 280 nm. From this data we calculate the band gap and Urbach energies of the materials produced.

Molecular Precursor Route to Bournonite (CuPbSbS3) Thin Films and Powders.

Quaternary metal chalcogenides have attracted attention as candidates for absorber materials for inexpensive and sustainable solar energy generation. One of these materials, bournonite (orthorhombic CuPbSbS3), has attracted much interest of late for its properties commensurate with photovoltaic energy conversion. This paper outlines the synthesis of bournonite for the first time by a discrete molecular precursor strategy. The metal dithiocarbamate complexes bis(diethyldithiocarbamato)copper (II) (Cu(S2CNEt2)2, (1)), bis(diethyldithiocarbamato)lead (II) (Pb(S2CNEt2)2, (2)), and bis(diethyldithiocarbamato)antimony (III) (Sb(S2CNEt2)3, (3)) were prepared, characterized, and employed as molecular precursors for the synthesis of bournonite powders and the thin film by solvent-less pyrolysis and spray-coat-pyrolysis techniques, respectively. The polycrystalline powders and thin films were characterized by powder X-ray diffraction (p-XRD), which could be indexed to orthorhombic CuPbSbS3. The morphology of the powder at the microscale was studied using scanning electron microscopy (SEM). Energy-dispersive X-ray spectroscopy (EDX) was used to elucidate an approximately 1:1:1:3 Cu/Pb/Sb/S elemental ratio. An optical band gap energy of 1.55 eV was estimated from a Tauc plot, which is close to the theoretical value of 1.41 eV.

Eu2+: A suitable substituent for Pb2+ in CsPbX3 perovskite nanocrystals?

Eu2+ is used to replace toxic Pb2+ in metal halide perovskite nanocrystals (NCs). The synthesis implies injection of cesium oleate into a solution of europium (ii) bromide at an experimentally determined optimum temperature of 130 °C and a reaction time of 60 s. Structural analysis indicates the formation of spherical CsEuBr3 nanoparticles with a mean size of 43 ± 7 nm. Using EuI2 instead of EuBr2 leads to the formation of 18-nm CsI nanoparticles, while EuCl2 does not show any reaction with cesium oleate forming 80-nm EuCl2 nanoparticles. The obtained CsEuBr3 NCs exhibit bright blue emission at 413 nm (FWHM 30 nm) with a room temperature photoluminescence quantum yield of 39%. The emission originates from the Laporte-allowed 4f7-4f65d1 transition of Eu2+ and shows a PL decay time of 263 ns. The long-term stability of the optical properties is observed, making inorganic lead-free CsEuBr3 NCs promising deep blue emitters for optoelectronics.

Doping Up the Light: A Review of A/B-Site Doping in Metal Halide Perovskite Nanocrystals for Next-Generation LEDs.

All-inorganic metal halide perovskite nanocrystals (PeNCs) show great potential for the next generation of perovskite light-emitting diodes (PeLEDs). However, trap-assisted recombination negatively impacts the optoelectronic properties of PeNCs and prevents their widespread adoption for commercial exploitation. To mitigate trap-assisted recombination and further enhance the external quantum efficiency of PeLEDs, A/B-site doping has been widely investigated to tune the bandgap of PeNCs. The bandgap of PeNCs is adjustable within a small range (no more than 0.1 eV) by A-site cation doping, resulting in changes in the bond length of Pb-X and the angle of [PbX6]4. Nevertheless, B-site doping of PeNCs has a more significant impact on the bandgap level through modification of surface defect states. In this perspective, we delve into the synthesis of PeNCs with A/B-site doping and their impacts on the structural and optoelectronic properties, as well as their impacts on the performance of subsequent PeLEDs. Furthermore, we explore the A-site and B-site doping mechanisms and the impact of device architecture on doped PeNCs to maximize the performance and stability of PeLEDs. This work presents a comprehensive overview of the studies on A-site and B-site doping in PeNCs and approaches to unlock their full potential in the next generation of LEDs.

Savonius wind turbine blade design and performance evaluation using ANN-based virtual clone: A new approach.

The drag based Savonius wind turbine (SWT) has shown immense potential for renewable power generation in built-up areas under complex urban wind conditions. While a series of studies have been conducted on improving SWT's efficiency, optimal performance has yet to be achieved using traditional design approaches such as experimental and/or computational fluid dynamics methods. Recently, artificial intelligence and machine learning have been widely used in design optimization. As such, an ANN-based virtual clone can be an alternative to traditional design methods for wind turbine performance determination. Therefore, the main goal of this study is to investigate whether ANN-based virtual clones are capable of determining the performance of SWTs with a shorter timeframe and minimal resources compared to traditional methods. To achieve the objective, an ANN-based virtual clone model is developed. Two sets of data (computational and experimental) are used to validate and determine the efficacy of the proposed ANN-based virtual clone model. Using experimental data, the model's fidelity is over 98%. The proposed model produces results in one-fifth the time of the existing simulation (based on the combined ANN + GA metamodel) method. The model also reveals the location of the dataset's optimized point for augmenting the turbine's performance.

Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts.

High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η10 of (∼255 mV).

A Low-Temperature Synthetic Route Toward a High-Entropy 2D Hexernary Transition Metal Dichalcogenide for Hydrogen Evolution Electrocatalysis.

High-entropy (HE) metal chalcogenides are a class of materials that have great potential in applications such as thermoelectrics and electrocatalysis. Layered 2D transition-metal dichalcogenides (TMDCs) are a sub-class of high entropy metal chalcogenides that have received little attention to date as their preparation currently involves complicated, energy-intensive, or hazardous synthetic steps. To address this, a low-temperature (500 °C) and rapid (1 h) single source precursor approach is successfully adopted to synthesize the hexernary high-entropy metal disulfide (MoWReMnCr)S2 . (MoWReMnCr)S2 powders are characterized by powder X-ray diffraction (pXRD) and Raman spectroscopy, which confirmed that the material is comprised predominantly of a hexagonal phase. The surface oxidation states and elemental compositions are studied by X-ray photoelectron spectroscopy (XPS) whilst the bulk morphology and elemental stoichiometry with spatial distribution is determined by scanning electron microscopy (SEM) with elemental mapping information acquired from energy-dispersive X-ray (EDX) spectroscopy. The bulk, layered material is subsequently exfoliated to ultra-thin, several-layer 2D nanosheets by liquid-phase exfoliation (LPE). The resulting few-layer HE (MoWReMnCr)S2 nanosheets are found to contain a homogeneous elemental distribution of metals at the nanoscale by high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) with EDX mapping. Finally, (MoWReMnCr)S2 is demonstrated as a hydrogen evolution electrocatalyst and compared to 2H-MoS2 synthesized using the molecular precursor approach. (MoWReMnCr)S2 with 20% w/w of high-conductivity carbon black displays a low overpotential of 229 mV in 0.5 M  H2 SO4 to reach a current density of 10 mA cm-2 , which is much lower than the overpotential of 362 mV for MoS2 . From density functional theory calculations, it is hypothesised that the enhanced catalytic activity is due to activation of the basal plane upon incorporation of other elements into the 2H-MoS2 structure, in particular, the first row TMs Cr and Mn.

Synthesis of ternary copper antimony sulfide via solventless thermolysis or aerosol assisted chemical vapour deposition using metal dithiocarbamates.

Copper antimony sulfide (Cu-Sb-S) has recently been proposed as an attractive alternative photovoltaic material due to the earth-abundant and non-toxic nature of the elements, high absorption coefficients and band gaps commensurate with efficient harvesting of solar photonic flux across multiple phases of Cu-Sb-S. These materials are therefore highly desirable and sustainable and scalable deposition techniques to produce them are of interest. In this paper, we demonstrate two facile, low-temperature and inexpensive techniques (solventless thermolysis and aerosol-assisted chemical vapor deposition (AACVD)) for the preparation of binary digenite (Cu1.8S), chalcocite (Cu2S) and stibnite (Sb2S3) and several phases of ternary copper-antimony-sulfide (Cu2xSb2(1-x)Sy, where 0 ≤ x ≤ 1). It was found that by utilising these different techniques and varying the ratio of Cu:Sb, pure phases of ternary chalcostibite (CuSbS2), fematinite (Cu3SbS4) and tetrahedrite (Cu12Sb4S13) can be achieved. Two single-source precursors were investigated for this purpose, namely the diethyldithiocarbamate (DTC) complexes of copper and antimony Cu(DTC)2 and Sb(DTC)3. These were decomposed both individually (to produce binary materials) and combined (to produce ternary materials) at different ratios. From the solventless thermolysis and AACVD methods, either particulate or thin film material was formed, respectively. These materials were then characterised by powder XRD, SEM, EDX and Raman spectroscopies to determine the crystalline phase, material morphology and uniformity of elemental composition. This analysis demonstrated that as the Cu-content increases, the phase of the ternary material changes from chalcostibite (CuSbS2) and fematinite (Cu3SbS4) at a low Cu:Sb ratio to tetrahedrite (Cu12Sb4S13) at a high Cu:Sb ratio.

Tin Sulfide (SnS) Films Deposited by an Electric Field-Assisted Continuous Spray Pyrolysis Technique with Application as Counter Electrodes in Dye-Sensitized Solar Cells.

The deposition of tin sulfide (SnS) nanostructured films using a continuous spray pyrolysis technique is reported with an electric field present at the nozzle for influencing the atomization and the subsequent film deposition. In the absence of the electric field, the X-ray diffraction pattern shows the orthorhombic phase of SnS with a crystallographic preferred orientation along the (040) plane. The application of the electric field results in significant improvement in the morphology and a reduction in surface roughness (28 nm from 37 nm). The direct optical band gap of the films deposited with and without the electric field is estimated to be 1.5 and 1.7 eV, respectively. The photothermal deflection spectroscopy studies show a lower energetic disorder (no Urbach tail), which indicates an annealing effect in the SnS films deposited under the electric field. The improvement in the film properties is reflected in the expected improvement in the power conversion efficiency (PCE) of dye-sensitized solar cells fabricated using the SnS film as a counter electrode. An enhancement of PCE from 2.07% for the film deposited without the electric field to 2.89% for the film deposited with the electric field shows the role of the electric field in the fabrication of improved SnS films.

Digital technologies, healthcare and Covid-19: insights from developing and emerging nations.

COVID-19 pandemic created a global health crisis affecting every nation. The essential smart medical devices/accessories, quarantine facilities, surveillance systems, and related digital technologies are in huge demand. Healthcare, manufacturing industries, and educational institutions need technologies that allow working from a safe location. Digital technologies and Industry 4.0 tools have the potential to fulfil these customized requirements during and post COVID-19 crisis. The purpose of this research is to provide understanding to healthcare professionals, government policymakers, researchers, industry professionals, academics, and students/learners of the paradigm of different Digital technologies, Industry 4.0 tools, and their applications during the COVID-19 pandemic. Digital technologies, Industry 4.0 tools and their current and potential applications have been reviewed. The use of different Digital technologies and Industry 4.0 tools is identified. Digital technologies and Industry 4.0 tools (3D Printing, Artificial Intelligence, Cloud Computing, Autonomous Robot, Biosensor, Telemedicine service, Internet of Things (IoT), Virtual reality, and holography) offer opportunities for effective delivery of healthcare service(s), online education, and Work from Home (WFH) environment. The article emphasises the usefulness, most recent development, and implementation of Digital technologies, Industry 4.0 techniques, and tools in fighting the COVID-19 pandemic worldwide.

Prediction of COVID-19 Cases from the Nexus of Air Quality and Meteorological Phenomena: Bangladesh Perspective.

An integrated approach was used to estimate the number of COVID-19 patients related to air quality and meteorological phenomena. Additionally, the air quality during pre-lockdown, lockdown, and post-lockdown stages of the COVID-19 pandemic was assessed to determine the effect of the infection containment measures taken in Bangladesh during the pandemic. The air quality was assessed based on measurements of nitrogen dioxide (NO2), sulfur dioxide (SO2), ozone (O3), carbon monoxide (CO), black carbon, particulate matter (PM2.5 and PM10), and aerosol optical depth. Time-averaged maps of these parameters have been generated from NASA's (National Aeronautics and Space Administration) website. Values of these parameters have also been collected from a continuous air monitoring station (CAMS) located in Bangladesh's north-western city Rajshahi. The comparison shows that lockdown during the pandemic has brought significant improvements in air quality. However, the improvement was not sustained, since rapid increases in the air pollutant concentrations were observed in the post-lockdown period. Furthermore, Pearson correlation coefficients between each air quality variable and the daily new COVID-19 case rates were calculated. Different meteorological variables during the same time periods were determined to observe the variation in Rajshahi city. Relationships of these variables with the case rates were also established. Additionally, statistical analyses of the obtained data have been conducted for the measured variables using the Kruskal-Wallis test to assess the differences in the observed data among the pre-lockdown, lockdown, and post-lockdown periods. Dunn's "Q" test was employed to test if the variables showed significance statistical difference during the Kruskal-Wallis test for pairwise comparisons. From the study, it has been observed that both meteorological variables and air quality parameters have significant relationship with daily new COVID-19 case rates. Both positive and negative associations of these parameters with the COVID-19 case rates have been observed. Very high air pollution has been observed in the post-lockdown period. Thus, it is recommended that appropriate authorities undertake corrective measures to protect the environment in cities with large populations. This study provides guidance for decision makers and health officials for future research and potentially reducing the spread of COVID-19.

Direct synthesis of nanostructured silver antimony sulfide powders from metal xanthate precursors.

Silver(I) ethylxanthate [AgS2COEt] (1) and antimony(III) ethylxanthate [Sb(S2COEt)3] (2) have been synthesised, characterised and used as precursors for the preparation of AgSbS2 powders and thin films using a solvent-free melt method and spin coating technique, respectively. The as-synthesized AgSbS2 powders were characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The crystalline AgSbS2 powder was investigated using XRD, which shows that AgSbS2 has cuboargyrite as the dominant phase, which was also confirmed by Raman spectroscopy. SEM was also used to study the morphology of the resulting material which is potentially nanostructured. EDX spectra gives a clear indication of the presence of silver (Ag), antimony (Sb) and sulfur (S) in material, suggesting that decomposition is clean and produces high quality AgSbS2 crystalline powder, which is consistent with the XRD and Raman data. Electronic properties of AgSbS2 thin films deposited by spin coating show a p-type conductivity with measured carrier mobility of 81 cm2 V-1 s-1 and carrier concentration of 1.9 × 1015 cm-3. The findings of this study reveal a new bottom-up route to these compounds, which have potential application as absorber layers in solar cells.

Structural Investigations of α-MnS Nanocrystals and Thin Films Synthesized from Manganese(II) Xanthates by Hot Injection, Solvent-Less Thermolysis, and Doctor Blade Routes.

Manganese(II) xanthate complexes of the form [Mn(S2COR)2(TMEDA)], where TMEDA = tetramethylethylenediamine and R = methyl (1), ethyl (2), n-propyl (3), n-butyl (4), n-pentyl (5), n-hexyl (6), and n-octyl (7), have been synthesized and structures elucidated using single-crystal X-ray diffraction. Complexes 1-7 were used as molecular precursors to synthesize manganese sulfide (MnS). Olelyamine-capped nanocrystals have been produced via hot injection, while the doctor blading followed by thermolysis yielded thick films. Free-standing polycrystalline powders of MnS are produced by direct thermolysis of precursor powders. All thermolysis techniques produced cubic MnS, as confirmed by powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy. Magnetic measurements reveal that the α-MnS nanocrystals exhibit ferromagnetic behavior with a large coercive field strength (e.g., 0.723 kOe for 6.8 nm nanocrystals).

Synthesis of indium oxide microparticles using aerosol assisted chemical vapour deposition.

Microparticles of indium oxide (In2O3) are deposited on glass substrates at 500 °C using aerosol assisted chemical vapour deposition (AACVD). The structural, morphological and optical properties of the as-deposited particles are reported.

Thin films of formamidinium lead iodide (FAPI) deposited using aerosol assisted chemical vapour deposition (AACVD).

Formamidinium lead iodide (CH(NH2)2PbI3, FAPI) thin films have been deposited on glass substrates at 150 °C using ambient pressure aerosol assisted chemical vapour deposition (AACVD). The films have been analysed by a range of techniques including powder X-ray diffraction (pXRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, and UV-Vis-NIR absorption spectroscopy. Sharp reflections in the pXRD pattern can be indexed to the α-phase of FAPI which confirms the crystallinity of the as-deposited film and reveals a preferred growth orientation along the (002) plane with respect to the substrate. High magnification SEM images show that the thin film is comprised of a network of intimately connected FAPI crystallites which form a mesoporous architecture. EDX mapping of lead and iodine emission peaks show that the Pb and I within these films are spatially co-localised. Optical measurements show as-deposited FAPI films have absorption onsets in the near infra-red with a direct bandgap value of 1.46 eV, suitable for single junction solar cells. Four-point probe measurement of as deposited films show that the electrical conductivity (σ) of the FAPI thin film is 5.2 × 10-7 S/cm, which is similar to FAPI thin films deposited by spin coating technique.

A molecular precursor route to quaternary chalcogenide CFTS (Cu2FeSnS4) powders as potential solar absorber materials.

In the present work we report on the synthesis of tetragonal stannite Cu2FeSnS4 powders using a solvent free melt method using a mixture of Cu, Fe, and Sn(ii)/Sn(iv) O-ethylxanthates heated at different temperatures. The as-synthesized powders were characterized by powder X-ray diffraction (p-XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), UV-Vis absorption spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, which confirm the successful synthesis of stannite CFTS. Optical measurements show that Cu2FeSnS4 powders have visible light absorption onsets in the far red with direct band gap energies in the range 1.32-1.39 eV which are suitable for acting as efficient absorber layers in solar cells. Electronic characterisation of these materials deposited as thin films by spin coating show that they are p type semiconductors with respectable carrier mobilities of ca. 60 cm2 V-1 s-1 with carrier densities on the order of 1014 cm-1.

Seasonal distribution and faunistic of ticks in the Alashtar county (Lorestan Province), Iran.

INTRODUCTION: Ticks are non-permanent obligate parasites that have considerable medical-veterinary and zoonosis importance. In this regard a study designed to investigate the distribution and fauna of ticks in the Alashtar county in Iran from April and March 2014. METHODS: Ticks were collected from livestock farms and facilities from selected rural and geographically location in the Alashtar county. Based morphological characteristics and reference identification keys, ticks were identified. RESULTS: A total of 549 ticks including 411 hard and 138 soft ticks were found. Ten tick species including Haemaphysalis concinna (0.36%), Haemaphysalis sulcata (0.36%), Hyalomma anatolicum (0.18%), Hyalomma dromedarii (0.18%), Hyalomma marginatum (1.45 %), Hyalomma schulzei (0.36%), Rhipicephalus annulatus (0.18%), Rhipicephalus bursa (28.1%), Rhipicephalus sanguineus (43.63%) and Argas persicus (25.2%) were identified. Tick seasonal distribution were 47.26%, 22.63%, 14.96% and 15.15% in the spring, summer, autumn and winter, respectively. The tick distribution was more from plain areas (64.96%) than the mountainous areas (35.04%). The rates of the tick contamination were 97.3% and 2.7% in the traditional and industrial livestock's, respectively. The livestock contamination ranks to the hard ticks were cattle (39.51%), sheep (34.15%) and goats (26.34 %), respectively. Chi-square analysis showed a significant difference among the seasonal distribution of the ticks in the spring, summer and autumn or winter; between the tick distribution in the plain and mountainous areas; and between the traditional and industrial livestock's tick contamination (P < 0.05). CONCLUSION: Present study proves to change the traditional livestock's to the industrial livestock's. These findings highlight the importance of ticks and shows need to their control and tick pest management.