A facile chemical conversion synthesis of Sb2S3 nanotubes and the visible light-driven photocatalytic activities

ABSTRACT: We report a simple chemical conversion and cation exchange technique to realize the synthesis of Sb2S3 nanotubes at a low temperature of 90°C. The successful chemical conversion from ZnS nanotubes to Sb2S3 ones benefits from the large difference in solubility between ZnS and Sb2S3. The as-grown Sb2S3 nanotubes have been transformed from a weak crystallization to a polycrystalline structure via successive annealing. In addition to the detailed structural, morphological, and optical investigation of the yielded Sb2S3 nanotubes before and after annealing, we have shown high photocatalytic activities of Sb2S3 nanotubes for methyl orange degradation under visible light irradiation. This approach offers an effective control of the composition and structure of Sb2S3 nanomaterials, facilitates the production at a relatively low reaction temperature without the need of organics, templates, or crystal seeds, and can be extended to the synthesis of hollow structures with various compositions and shapes for unique properties.     

Optoelectronic properties of Zn-doped Cu3Se2 nanosheets for photovoltaic application

Thin films of Zn-doped copper selenide (Cu₃Se₂) nanostructures with different Zn concentrations were deposited on fluorine-doped tin oxide (FTO) glass substrates by electrodeposition method. The structural, optical, electrical, and photovoltaic properties of the deposited films were investigated by different analyses. X-ray diffraction (XRD) pattern showed the crystalline and tetragonal structure of the samples. The results of XRD pattern also showed that the peaks shifted to higher angles by increasing the Zn dopant, indicating the influence of dopant on the crystalline structure of Cu₃Se₂. Electron microscopy analysis showed that the films had a sheet-like shape whose thickness changed by altering the dopant percentage; the highest number of sheets belonged to the samples with higher concentrations of dopant. The photoluminescence (PL) analysis of the Cu₃Se₂ nanostructures revealed that the peaks in the green and infrared regions shifted to shorter wavelengths and the intensity of emission peaks increased for the Zn-doped sample with the highest concentration, compared with the un-doped sample. Based on the absorption spectrum analysis, the optical energy band gap increased with raising the percentage of Zn dopant. Finally, the electrical and photovoltaic parameters of the solar cells prepared via Cu₃Se₂ nanosheets were examined. The doped sample which had the highest percentage of doping, showed the highest efficiency (η) of ~1.30%.     

Influence of the selenization time on the properties of (Na0.1Cu0.9)2ZnSn(S,Se)4 thin films and their photovoltaic solar cells

(Na_0.1Cu_0.9)₂ZnSn(S,Se)₄ thin films with a single kesterite phase were synthesized using a sol-gel spin-coating method accompanied by rapid post-annealing. In this study, we investigated the effect of selenization time on the crystal quality and photoelectric performance of the (Na_0.1Cu_0.9)₂ZnSn(S,Se)₄ films. It was found that the crystallinity and morphology of the films was enhanced, and some of bigger Se substituted for the S site in (Na_0.1Cu_0.9)₂ZnSn(S,Se)₄ with increasing the selenization time. The bandgap of the film can be regulated from 1.04 eV to 0.99 eV by varying the selenization time. In addition, all films showed p-type conductive characteristics, and films with optimal electrical performance could be obtained by optimizing the selenization time. Finally, the (Na_0.1Cu_0.9)₂ZnSn(S,Se)₄ thin film with the best crystal quality and optical-electrical characteristics was obtained at an optimized selenization time of 15 min. A high power conversion efficiency (PCE) of 3.92% was obtained for the (Na_0.1Cu_0.9)₂ZnSn(S,Se)₄ device, which is 42% higher compared to that of the undoped Cu₂ZnSn(S,Se)₄ (CZTSSe) device.     

The effect of the Zn/Sn ratio on the formation of single phase kesterite Cu2ZnSnS4 solar cell material

The effect of the Zn/Sn ratio in the solution on the properties of Cu₂ZnSnS₄ films prepared by sol-gel method has been investigated. As the Zn/Sn ratio in the solution increases to a certain value, a pure single phase kesterite CZTS is obtained and confirmed by XRD, XPS and Raman. Through controlling the Zn/Sn ratio in the solution, secondary phases such as SnO₂ can be avoided and an optimal condition for single phase kesterite CZTS can be achieved. Surface SEM images of the CZTS films are investigated and the optical band gap of the optimized CZTS film is found to be 1.23 eV.     

Optimization of methane cold wall chemical vapor deposition for the production of single walled carbon nanotubes and devices

Carbon nanotubes are synthesized by cold wall chemical vapor deposition (CVD) using methane as the carbon source and iron thin film catalyst. The yield of thin nanotubes as determined by scanning electron microscopy (SEM) is strongly dependent on the precise CVD process and the preparation of the substrate. The effects of pressure (5–80 kPa), temperature (700–950 °C), substrate conditioning (air preheat) and metallization (Fe, Al, Mo) on thin nanotube yield are reported. High yields of thin nanotubes are obtained under optimum conditions. These thin nanotubes are candidates to be single walled carbon nanotubes (SWNTs) and Raman spectroscopy, photoluminescence spectroscopy and electrical transport provide evidence that, at least at optimum conditions, many, and perhaps all of the thin nanotubes are single walled. Single nanotube field effect transistors are fabricated and factors affecting device yield are reported. Optimum single nanotube device yield does not necessarily coincide with the optimum nanotube yield.     

Polarization dependent optical absorption properties of single-walled carbon nanotubes and methodology for the evaluation of their morphology

Polarization dependence of the optical absorption properties of SWNTs is presented and investigated in detail for the energy range 0.5-6 eV. We found that the absorption peaks in the UV region at approximately 4.5 and 5.25 eV exhibit remarkable and different dependencies on the morphology of the SWNT film, or equivalently, on the incident light polarization relative to the SWNT axis. An analytical pathway to evaluate the physical degree of SWNT alignment for a vertically aligned SWNT film is developed with both transition dipoles parallel and perpendicular to the SWNT axis taken into account. This analytical procedure, coupled with polarized optical absorption measurements performed on the vertically aligned SWNT film grown on substrates, leads to the determination of the bare optical absorption cross-section of SWNTs for both parallel and perpendicular to SWNT axis. In the end, the proposed methodology for evaluating the SWNT film morphology is applied to investigate the transient change of the degree of alignment in the growth process of our vertically aligned SWNT films.     

Spray-deposited kesterite Cu2ZnSnS4 (CZTS): Optical,structural, and electrical investigations for solar cell applications

Kesterite Cu₂ZnSnS₄ (CZTS)-based solar devices have become a popular alternative to copper indium gallium selenide (CIGS) due to its outstanding properties such as high efficiency, non-toxicity, cost-effectiveness, suitable optoelectrical properties, and earth-abundancy. In this study, we directly fabricated CZTS films via a single-step spray pyrolysis technique, in contrast to conventional techniques where post sulfurization is required. The spray deposited CZTS films are investigated for their optical, structural, and electrical properties. The X-ray diffraction (XRD) and Raman analysis study revealed the synthesis of the phase-pure kesterite CZTS films without impurity phases. Large crystallites of CZTS are obtained at a deposition temperature of 400 °C, exhibiting a porous granular morphology with different grain sizes upon temperature variation. The size-dependent optical properties revealed that the CZTS films exhibited admirable visible light absorption of 10⁵ cm^?1 and an electronic bandgap ranging between 1.42 and 1.58 eV. The minimum dielectric loss obtained for optimized CZTS due to fewer intrinsic defects confirmed the materials’ applicability. Thus, the study provides a simple, viable route to fabricate CZTS without post-treatment to build affordable solar cells.     

Influence of NH3·H2O additive on the photovoltaic performance of dye-sensitized solar cells with chemical sintered scattering layers

A bi-functional nanocrystalline TiO₂ (nc-TiO₂) layer able to offer both light-scattering and electron generating properties was prepared with a simple method through adding the basic NH₃·H₂O agent into an acid nc-TiO₂ paste to form some big rod-like nc-TiO₂ aggregates by the chemical sintering process. The influence of additional amount of NH₃·H₂O on the photovoltaic performance of the dye-sensitized solar cell with this bi-functional nc-TiO₂ layer in the photoelectrode was studied. It was found that through controlling the additional amount of NH₃·H₂O and the thickness of the bi-functional nc-TiO₂ layer, the highest energy conversion efficiency about 8.11% could be obtained, which was much higher than that of the dye-sensitized solar cell containing a single nc-TiO₂ layer prepared with the original acid nc-TiO₂ paste (4.34%).     

Growth and properties of Cu3SbS4 thin films prepared by a two-stage process for solar cell applications

Cu₃SbS₄ is a promising material for thin film heterojunction solar cells owing to its suitable optical and electrical properties. In this paper, we report the preparation of Cu₃SbS₄ thin films by annealing the Sb₂S₃/CuS stacks, produced by chemical bath deposition, in a graphite box held at different temperatures. The influence of annealing temperature on the growth and properties of these films is investigated. These films are systematically analyzed by evaluating their structural, microstructural, optical and electrical properties using suitable characterization techniques. X-ray diffraction analysis showed that these films exhibit tetragonal crystal structure with the lattice parameters a=0.537 nm and b=1.087 nm. Their crystallite size increases with increasing annealing temperature of the stacks. Raman spectroscopy analysis of these films exhibited modes at 132, 247, 273, 317, 344, 358 and 635 cm⁻¹ due to Cu₃SbS₄ phase. X-ray photoelectron spectroscopy analysis revealed that the films prepared by annealing the stack at 350 °C exhibit a Cu-poor and Sb-rich composition with +1, +5 and −2 oxidation states of Cu, Sb and S, respectively. Morphological studies showed an improvement in the grain size of the films on increasing the annealing temperature. The direct optical band gap of these films was in the range of 0.82–0.85 eV. Hall measurements showed that the films are p-type in nature and their electrical resistivity, hole mobility and hole concentration are in the ranges of 0.14–1.20 Ω-cm, 0.05–2.11 cm² V⁻¹ s⁻¹ and 9.4×10²⁰–1.4×10¹⁹ cm⁻³, respectively. These structural, morphological, optical and electrical properties suggest that Cu₃SbS₄ could be used as an absorber layer for bottom cell in multi-junction solar cells.     

Influence of synthesis parameters on the physical properties of Cu3Se2 nanostructures using the sonochemical method

Copper selenide (Cu₃Se₂) nanostructures were grown by reaction of copper acetate and sodium selenide in a solvent of distilled water and ethanol at a temperature of 80 °C using the sonochemical method. In this study, the change of molarity, time, and power of ultrasonication waves was investigated on the physical properties of Cu₃Se₂ nanostructures. Cu₃Se₂ nanostructures were characterized by X-ray diffraction (XRD) patterns, field emission scanning electron microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDX), photoluminescence (PL), and UV–Vis spectroscopies. In this study the optimized conditions were selected as 30 min, 200 W, 1:2 for time, ultrasonic power, and molar ratio of Cu:Se, respectively. The XRD patterns and EDX results represent the formation of tetragonal Cu₃Se₂ phase and the presence of Cu and Se elements in the samples. FESEM images showed nanostructures in the form of spherical agglomerated particles. The results of the PL showed the effect of time, power, and molarity parameters on the appearance of different emission peaks. In all samples, the relative absorption ratio corresponded to the energy band gap such that with the increase in the time and power of ultrasound and the relative change in molarity, the relative absorption, and energy band gap were changed.     

The effect of transition metal ions (M2+=Mn2+, Ni2+, Co2+, Cu2+) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M~(2+)=Mn~(2+),Ni~(2+),Co~(2+),Cu~(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I~-/I_3~-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn~(2+),Ni~(2+),Co~(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu~(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu~(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni~(2+), PANI-Co~(2+),PANI-Mn~(2+) and PANI-Cu~(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M~(2+)=Mn~(2+),Ni~(2+),Co~(2+),Cu~(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.     

Influence of total pressure on the microstructures and growth mechanism of ZrC coatings prepared by chemical vapor deposition from the Zr-Br2-C3H6-H2-Ar system

Zirconium carbide (ZrC) coatings were deposited on graphite substrates by chemical vapor deposition from the Zr-Br₂-C₃H₆-H₂-Ar system. The influence of total pressure on the growth of ZrC was investigated in the range of 5–60 kPa. As the total pressure increased, the deposition rate increased evidently, and the preferential orientation of ZrC coatings changed from the (200) plane to the (220) plane. The growth mechanism changed from a mass transport reaction to a surface reaction at the total pressure of 20–40 kPa. At the total pressure below 20 kPa, the deposition was dominated by crystal growth, so the coatings were composed of well-faceted pyramidal-shaped crystals growing along the <001> direction. At the total pressure above 60 kPa, the growth of ZrC coatings was controlled by the nucleation mechanism, so the coatings were cluster-like crystals rapidly growing along the <110> direction. In addition, low pressure was conducive to the formation of near-stoichiometric ZrC without free carbon. These variations of ZrC coatings can mainly be attributed to gas supersaturation and remarkably changed transport diffusion coefficients with increasing total pressure.     

Synthesis and investigation of environmental protection and earth-abundant kesterite Cu2MgxZn1-xSn(S,Se)4 thin films for solar cells

We have synthesized Cu₂Mg_xZn_1–xSn(S,Se)₄ (0?≤?x?≤?0.6) thin films by a facile sol-gel method, and studied the influence of Mg concentration on the crystal structure, surface morphology and photoelectric performance of Cu₂Mg_xZn_1–xSn(S,Se)₄ thin films systematically. It was shown that the smaller Zn²⁺ in Kesterite phase Cu₂ZnSn(S,Se)₄ will be replaced by larger Mg²⁺, forming uniform pure phase Cu₂Mg_xZn_1–xSn(S,Se)₄. The band gap of Cu₂Mg_xZn_1–xSn(S,Se)₄ films can be adjusted from 1.12 to 0.88?eV as the x value changes from 0 to 0.6. Furthermore, the Cu₂Mg_xZn_1–xSn(S,Se)₄ thin films with large grain size, smooth surface and less grain boundaries was obtained at an optimized condition of x?=?0.2. The carrier concentration of Cu₂Mg_xZn_1–xSn(S,Se)₄ thin film reaches the maximum 6.47?×?10¹⁸ cm^?3 at x?=?0.2, which is a potential material to be the absorption layer of high efficiency solar cells.     

Synthesis and characterization studies of NiO nanorods for enhancing solar cell efficiency using photon upconversion materials

We report the effect of calcination on the structural and optical properties of nanocrystalline NiO nanoparticles were successfully synthesized by virtue of a single source precursor method at mild reaction conditions between nickel nitrate and sodium hydroxide. Composition, structure and morphology of the products were analyzed and characterized by X-ray powder diffraction (XRD). The ultra-violet visible (UV–vis) absorption peaks of NiO exhibited a large blue shift and the luminescent spectra had a strong and broad emission band centered at 328 nm. The intense band gap was also observed, with some spectral tuning, to give a range of absorption energies from 2.60 to 3.41 eV. The various functional groups present in the NiO nanorods were identified by FTIR analysis. High resolution transmission electron microscopy (HRTEM) and the chemical composition of the samples the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS) in detail. The electrochemical response of NiO proved that the nano-nickel has a high level of functionality due to its small size and higher electrochemical activity without any modifications. The above studies demonstrate the potential for the utilization of NiO nanoparticles as a promising material for opto-electronics applications.     

Systematic study of optoelectronic and transport properties of cesium lead halide (Cs2PbX6; X=Cl,Br, I) double perovskites for solar cell applications

A systematic density functional theory investigation of Cs₂PbX₆ (X = Cl, Br, I) double perovskites is presented. The lattice constants are computed after structure optimization and using Birch-Murnaghan equations, which agree to the experimental literature. The mechanical stability conditions satisfy Born criteria, and the ductile nature is evidenced by the calculated Poisson's (v) and Pugh's ratios (B₀/G) because all three double perovskites exhibit values higher than the respective critical values v = 0.26 and B₀/G = 1.75. A detailed study of the optoelectronic properties reveals these double perovskites as promising candidates for future optical devices due to their direct band gaps (within 0.45–2.54 eV) and large absorption coefficients 5.95 × 10⁵ cm⁻¹, which are suitable for solar cell applications. ZT calculations demonstrate minute variations within 200–800 K and computed parameter values are quite favorable for thermoelectric applications of these materials in the future. A p-type semiconducting nature is predicted by the computed thermoelectric properties. Additionally, computed refractive indices show Cs₂PbBr₆ and Cs₂PbI₆ exhibiting super-luminescent properties in the UV range. Therefore, the studied double perovskites provide further interest for future energy conversion and photonic based technologies.     

A new approach for the combined chemical and mineral classification of the inorganic matter in coal. 2. Potential applications of the classification systems

Part 1 of the present work introduced and evaluated a new approach for the combined chemical and mineral classification of the inorganic matter in coal. The benefit of these classification systems is the use of significant correlations and actual element associations, and well-defined and genetically described mineral classes and species in coal. Potential applications of the chemically and mineralogically categorized coal types and subtypes are discussed in the present part 2. The data show that various technological problems, environmental risks and health concerns of coal use are related directly or indirectly to specific mineral and chemical coal types and subtypes. Furthermore, a concept of “self-cleaning fuels” also is introduced and developed herein based on mineral coal types. The application of these chemical and mineral classification systems and concept is proposed to both the scientific and industrial community.     

Emulsifying and foaming properties of native and chemically modified peptides from the 2S and 12S proteins of rapeseed (Brassica napus L.)

The 2S and 12S proteins of rapeseed were isolated and subsequently hydrolyzed by pepsin or a combination of pepsin plus trypsin. The resulting hydrolysates had a 15% degree of hydrolysis and were purified by gel filtration chromatography in order to obtain homogeneous peptide fractions. Three major fractions, having an average peptide chain length of 7.5–11 amino acids, were recovered. Purified peptide fractions were acylated with butyric anhydride and sulfamidated with p-toluenesulfonyl chloride. The degree of modification was always higher than 90%. Emulsifying and foaming properties of native and chemically modified peptides were studied and compared to those of sodium dodecyl sulfate (SDS) as standard. A peptide fraction from the 15% hydrolysis of the 12S protein exhibited the best foaming properties. After sulfamidation, this peptide fraction showed a foam formation similar to that of SDS. Whereas the attachment of toluene groups generally improved the surface properties, the incorporation of an aliphatic chain of four atoms of carbon was detrimental in most of the cases. On the other hand, none of the native or hydrophobized peptide fractions was able to form a stable emulsion.     

Thermal Evaporation Synthesis and Properties of ZnO Nano/Microstructures Using Carbon Group Elements as the Reducing Agents

ZnO nano/microstructures have been formed by thermal evaporation method using ZnO powders mixed with carbon group elements (C, Si, Ge, Sn, or Pb) as the reducing agent. For cases of mixed precursors of ZnO/C, ZnO/Si, and ZnO/Ge, the pure ZnO nano/microstructures are realized, while for ZnO/Sn (ZnO/Pb) systems, the phase of Pb₂O₃ (Zn₂SnO₄) generally are represented in the ZnO products. The appearance of Pb₂O₃ (Zn₂SnO₄) is attributed to the lower melting point and higher vapor pressure of Sn (Pb) in the heating and evaporation processes. The morphologies and sizes of the products are controlled by adjusting the growth regions and/or introducing gaseous argon. Room temperature (RT) photoluminescence spectra indicate that the intensity (peak position) of the ultraviolet emission is increased (redshift) due to the existence of Zn₂SnO₄ phase in the ZnO products. The Pb₂O₃ (Zn₂SnO₄) phase in ZnO nano/microstructures plays a important role in enhancing the saturation magnetizations of RT ferromagnetism with respect to the case of pure ZnO products fabricated by the precursor of mixed ZnO and graphite.     

Analysis of optoelectronic and trasnport properties of magnesium based MgSc2X4 (X=S,Se) spinels for solar cell and energy storage device applications

Intense research work is underway for identifying materials with potential applications in energy storage and energy harvesting systems. The magnesium based scandium chalcogenides have recently emerged as potential candidates for Mg batteries owing to their high Mg ionic conductivity and low electron conduction. At the same time, their band gaps are capable of absorbing electromagnetic radiations in visible to UV range; making them suitable for solar cell applications. In order to analyze the application of MgSc₂X₄(X = S, Se) compounds in energy devices, in this work we employ density functional theory calculations using the full potential linear augmented plane-wave method for examining their optoelectronic and thermoelectric properties. For the structural properties, the generalized gradient approximation functional designed for solids (PBEsol-GGA) has been used, while modified Becke and Johnson (mBJ) potential functional is used for computing the optoelectronic and transport properties. Our calculated optical properties indicate that these materials can find applications in solar cells. Moreover, the electronic transport properties computed using Boltzmann transport equation suggest carrier concentrations in MgSc₂S₄ to MgSc₂Se₄ spinels can be tuned for making them suitable for metal ion batteries.     

A new approach for the combined chemical and mineral classification of the inorganic matter in coal. 1. Chemical and mineral classification systems

This work introduces and evaluates a new approach for the combined chemical and mineral classification of the inorganic matter in coal. Thirty-seven coal samples from Australia, Bulgaria, USA, Japan, Canada, South Africa, China, Spain, and Ukraine, which differ considerably in their geology, rank, age, ash yield, chemistry and mineralogy, were used to establish the classifications. The chemical classification system was organized according to the contents and significant positive or negative correlations of ash-forming elements in coal ashes using three composition-based criteria, namely: (1) sum of Si, Al, K, and Ti oxides; (2) sum of Ca, Mg, S, and Na oxides; and (3) Fe oxide. This approach resulted in four chemical coal ash types (sialic, calsialic, ferrisialic, and ferricalsialic) further divided into seven subtypes (with high, medium and low acid tendencies) based on the sum of Si, Al, K, and Ti oxides. The more important mineral classification system was organized according to the contents, genesis, and behaviour of mineral classes and species in coals also using three composition-based criteria, namely: (1) silicates + oxyhydroxides; (2) carbonates; and (3) sulphides + sulphates + phosphates. This approach resulted in four mineral coal types (silicate, silicate-carbonate, silicate-sulphide, and silicate-sulphide-carbonate or mixed) further divided into seven subtypes (with high, medium and low detrital tendencies) based on the sum of silicates and oxyhydroxides. The chemical and mineral coal types and subtypes are characterized and relationships and distinctions between them also are described herein. The benefit of this new classification approach is the use of significant correlations and actual element associations, and well-defined and genetically described mineral classes and species in coal. Potential applications of the classification schemes are described in part 2 of the present work.