Copper Sulfide Nanostructures Research Articles

Phase pure deposition of flower-like thin films by aerosol assisted chemical vapor deposition and solvent mediated structural transformation in copper sulfide nanostructures

Bis(O-isobutyldithiocarbonato)copper(II) complex [Cu(SCSOCH2CH(CH3)2)2] was used as a single source precursor to synthesize both copper sulfide thin films and nanoparticles. The copper sulfide thin films were deposited by the aerosol assisted chemical vapor deposition method, whereas the nanoparticles were synthesized by the hot injection route. The deposited copper sulfide thin films showed different morphologies based on spherical to flower or flakes-like crystallites depending on the temperature of deposition. Powder X-ray diffraction studies of the deposited films revealed formation of pure Covellite-hexagonal phase of copper sulfide, with high crystallinity at elevated temperature. The diffraction pattern of nanoparticles synthesized in dodecanthiol, and 1-octadecene at 150°C, 190°C and 230°C showed the formation of monodispersed nanoparticles of Cu1.78S Roxbyite phase with an average size of ca. 12±1nm. Interestingly, when oleylamine was used as a capping solvent, the formation of Covellite and Digenite phases were obtained at temperatures of 110°C and 190°C respectively. Electron microscopic studies showed formation of rod shaped particles at 110 and 150°C, whereas at higher temperatures formation of fairly spherical nanoparticles were observed.

Eco-friendly synthesis and morphology-dependent superior electrocatalytic properties of CuS nanostructures

Copper sulfide with desired structure is of special interest for electrocatalytical application due to their unique physicochemical properties, simple synthesis and less toxic in nature. In this study, simple and eco-friendly (without using any template or surfactant) route for the fabrication of copper sulfide nanostructure morphologies were tuned from cauliflower, microflower to nanoparticles inter-connected network-like structures by changing the polarity of solvent medium during solvothermal synthesis. However, to the best of our knowledge, no such kinds of special three types of CuS nanostructure with excellent electro-catalytic properties using only H2O and C2H5OH as the solvents have been reported in the literature. The as-prepared different CuS nanostructure was characterized using FE-SEM, HR-TEM, XRD, XPS and cyclic voltammetry. This morphological alteration able to produce several precise nanostructures with improved electrocatalytic properties that led to an excellent performance towards enzymeless glucose oxidation. The CuS inter-connected nanoparticles modified electrode displayed a synergistic effect towards the oxidation of glucose (ipa: 103±5μA) when compared to that of cauliflower (ipa: 68±3.7μA) and microflower (ipa: 60±2.4μA) modified electrode surfaces. Further, the CuS inter-connected nanoparticles modified electrode showed a wide linear range (2.0×10−5−2.5×10−3M), high sensitivity (1085μAmM−1cm−2), low detection limit (2μM), rapid response time (<3s), good stability, selectivity and reproducibility. The obtained sensing parameters based on CuS inter-connected nanoparticles modified electrode were superior with many reports and also comparable with few reports in the available literatures.

Facile and controlled synthesis of copper sulfide nanostructures of varying morphology

Copper sulfide nanostructures with different morphology have been developed using wet chemical route. The product so obtained have been characterized using X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Ultraviolet visible spectroscopy (UV–Vis) and photoluminescence (PL) technique. Effect of reaction medium on the morphology of the obtained samples has been studied in detail. We hereby demonstrate that while the reaction medium used has no impact on the phase of the prepared sample, however it plays an important role in deciding the morphology. CuS nanoparticles, nanoflower and nanoflakes like structure have been prepared under optimized condition using facile method in small period of time.

Plasmon Enhanced Direct Bandgap Emissions in Cu7 S4 @Au2 S@Au Nanorings.

Nanostructured copper sulfides, promising earth-abundant p-type semiconductors, have found applications in a wide range of fields due to their versatility, tunable low bandgap, and environmental sustainability. The synthesis of hexagonal Cu7 S4 @Au2 S@Au nanorings exhibiting plasmon enhanced emissions at the direct bandgap is reported. The synthesized Cu7 S4 @Au2 S@Au nanorings show greatly enhanced absorption and emission by local plasmons compared to pure copper sulfide nanoparticles.

Integration of Semiconducting Sulfides for Full‐Spectrum Solar Energy Absorption and Efficient Charge Separation

AbstractThe full harvest of solar energy by semiconductors requires a material that simultaneously absorbs across the whole solar spectrum and collects photogenerated electrons and holes separately. The stepwise integration of three semiconducting sulfides, namely ZnS, CdS, and Cu2−xS, into a single nanocrystal, led to a unique ternary multi‐node sheath ZnS–CdS–Cu2−xS heteronanorod for full‐spectrum solar energy absorption. Localized surface plasmon resonance (LSPR) in the nonstoichiometric copper sulfide nanostructures enables effective NIR absorption. More significantly, the construction of pn heterojunctions between Cu2−xS and CdS leads to staggered gaps, as confirmed by first‐principles simulations. This band alignment causes effective electron–hole separation in the ternary system and hence enables efficient solar energy conversion.

Integration of Semiconducting Sulfides for Full-Spectrum Solar Energy Absorption and Efficient Charge Separation.

The full harvest of solar energy by semiconductors requires a material that simultaneously absorbs across the whole solar spectrum and collects photogenerated electrons and holes separately. The stepwise integration of three semiconducting sulfides, namely ZnS, CdS, and Cu2-x S, into a single nanocrystal, led to a unique ternary multi-node sheath ZnS-CdS-Cu2-x S heteronanorod for full-spectrum solar energy absorption. Localized surface plasmon resonance (LSPR) in the nonstoichiometric copper sulfide nanostructures enables effective NIR absorption. More significantly, the construction of pn heterojunctions between Cu2-x S and CdS leads to staggered gaps, as confirmed by first-principles simulations. This band alignment causes effective electron-hole separation in the ternary system and hence enables efficient solar energy conversion.

A single precursor route to synthesize CuO and CuS nanostructures based on copper ammine and thiourea complexes

The hydrothermal synthesis is reported of copper(II) oxide and copper(II) sulfide nanostructures with different morphologies using ammine (NH3) and thiourea (tu) complexes of copper(I) and copper(II) as the starting materials in the absence of any capping agents/surfactants. Indeed, ammine and thiourea ligands act as the sources of hydroxide and sulfur ions in the preparation of CuO and CuS nanostructures, respectively, as well as central copper ion as the Cu source. This method has the advantages of the simplicity and low cost. The synthesized products were characterized by X-ray diffraction, Fourier transformation infrared spectroscopy and scanning electron microscopy techniques. Further, the effects of precursor concentration, temperature and reaction time on the morphology and size of the nanostructures were studied.

Fabrication and applications of copper sulfide (CuS) nanostructures

This review article presents different fabrication procedures (under the headlines of solvothermal routes, aerosol methods, solution methods and thermolysis), and applications (photocatalytic degradation, ablation of cancer cells, electrode material in lithium ion batteries and in gas sensing, organic solar cells, field emission properties, super capacitor applications, photoelectrochemical performance of QDSCs, photocatalytic reduction of organic pollutants, electrochemical bio sensing, enhanced PEC characteristics of pre-annealed CuS film electrodes) of copper sulfide (Covellite).

Facile and Novel Chemical Synthesis, Characterization, and Formation Mechanism of Copper Sulfide (Cu2S, Cu2S/CuS, CuS) Nanostructures for Increasing the Efficiency of Solar Cells

This paper reports the successful synthesis of various copper sulfide nanostructures via coprecipitation and hydrothermal routes using new starting reagents such as Na2SO3 as a reducing agent for converting Cu2+ to Cu+ and PMP dye–Cu(II) and carminic acid–Cu(II) complexes as new copper precursors for synthesizing quantum dots in aqueous medium. The as-synthesized products were extensively characterized by techniques including XRD, EDS, SEM, TEM, AFM, and DRS. Effects of different parameters such as temperature, surfactant, solvent, concentration, copper precursor, sulfide source, etc., on morphology and particle size of as-synthesized nanostructures were investigated. Moreover, the efficiency of various as-synthesized nanostructures in thin layer solar cells was evaluated. The results showed that particle size and morphology have a salient effect on solar cell efficiency. Also, utilizing prepared Cu2S quantum dots as a barrier layer in dye-sensitized solar cells (DSSCs) presented a remarkable increase in ...

Nanostructured copper sulfides: synthesis, properties and applications

Copper sulfides are the most extensively studied materials due to their non-toxicity, semiconducting nature and tunable properties. In view of this, present review article discusses various synthetic strategies for the fabrication of nanostructured copper sulfides of different morphologies and properties comprehensively followed by their applications in various fields.

Water soluble sodium sulfate nanorods as a versatile template for the designing of copper sulfide nanotubes.

The present study reports the use of water soluble sodium sulfate (Na2SO4) nanorods as a versatile template for generation of tubular copper sulfide (CuS) nanostructures. The Na2SO4 nanorods were synthesized from ammonium sulfate (NH4)2SO4 and sodium hydroxide (NaOH), under refluxing condition. The shape and morphology control of the Na2SO4 nanorods were studied with respect to nature of surfactant used and reactant mole ratio. While, PVP mole ratio was important to obtain homogeneous nanorods. Uniform and stable nanotubes of CuS were than obtained by the dissolution of the nanorods in water. The use of simple chemicals for synthesis of such nanotube templates opens the prospect for wide scale downstream applications.

Synthesize Thickness Copper (I) Sulfide nanoplates on Copper Rod and It's Application as Nonenzymatic Cholesterol Sensor

Special rose-like copper (І) sulfide nanostructure (Cu2S NRS) made up of thickness nanoplates were successfully synthesized on copper rod by a simple method. Then the as-prepared Cu2S NRS/Cu rod can be used as integrated electrode (called as Cu2S NRS/CRIE) to nonenzymatic detect the cholesterol (CT). The electrochemical properties show these integrated electrode revealed wide linear range from 0.01mM to 6.8mM and low detection limit of 0.1μM (S/N=3) for the detection of cholesterol. What's more, the proposed sensor displays excellent selectivity, good stability, and satisfying repeatability.

Facile and low temperature route to synthesis of CuS nanostructure in mesoporous material by solvothermal method

The synthesis of CuS nanomaterial in MCM-41 matrix has been realized by chemical synthesis between MCM-41, copper sulfate pentahydrate and thiourea via a solvothermal method in ethylene glycol and water, separately. X-ray diffraction analysis (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and fourier transform infrared (FT-IR) were used to characterize the products. At synthesized CuS/MCM-41 sample in ethylene glycol, X-ray diffraction and diffuse reflectance spectroscopy showed pure covellite phase of copper sulfide with high crystality. But prepared CuS/MCM-41 sample in water shows the covellite, chalcocite and the djurleite phase of copper sulfide nanostructures. The formation of CuS nanostructures was confirmed by FT-IR. Photocatalytic activity of CuS/MCM-41 nanocomposites was studied for degradation of Methylene Blue (MB) under visible light. The CuS/MCM-41 nanocomposite is more effective nanocatalyst than synthesized CuS/MCM-41 sample in water for degradation of methylene blue. Several parameters were examined, catalyst amount (0.1–1gL−1), pH (1–13) and initial concentration of MB (0.96–10ppm). The extent of degradation was estimated from the residual concentration by spectrophotometrically. The support size was obtained in the range 60–145nm by TEM. In the same way, the average size of copper sulfide in CuSMCM-41E and CuS/MCM-41W nanostructures were obtained about 10nm and 16nm, respectively.

Electrochemical Synthesis of Copper Sulfide Nanostructure with PAM Hydrogel Template

Flower-like, sphere and lamellar structures of copper sulfide have been prepared by an electrochemical method with PAM hydrogel as template. The unique synthetic method required no multiple growth steps typical of other methods, and just utilized the electric currents to drive the ions to realize the controlling the resultant morphology in the PAM hydrogel system. The structure of product was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The morphology of these structures could be controlled by adjusting the content of PAM in hydrogel, and the intension of electric current.

Semiconducting nanostructured copper sulfide thin films from bidentate copper(ii) complexes of N-(dialkylcarbamothioyl)-nitrosubstituted benzamides by chemical vapour deposition

Copper(II) complexes of various N-(dialkylcarbamothioyl)-nitrosubstituted benzamide [dialkyl = di-n-butyl (1a, 2a); hexyl, methyl (3a); butyl, ethyl (4a)] have been synthesized and characterized by elemental analysis, IR spectroscopy and atmospheric pressure chemical ionization-mass spectrometry (MS-APCI). The molecular structure of the complex 2a was determined by single-crystal X-ray diffraction. These complexes were used as single-source precursors for the deposition of copper sulfide thin films by aerosol assisted chemical vapour deposition (AA-CVD) at 350 °C. The powder X-ray diffraction (p-XRD) patterns of the thin films of complexes 3a and 4ashowed the deposition of rhombohedral digenite Cu9S5 phase, and complex 1a deposited monoclinic roxbyite Cu7S4 phase at 350 °C with spherical crystallites. Complex 2a deposited orthorhombic anilite Cu7S4 phase with spherical crystallites. The degree of roughness of the film surface was determined by atomic force microscopy (AFM). The scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) results showed the uniform distribution of copper sulfide in the films, which makes them useful semiconducting materials on a structured surface.

Sonochemical preparation of copper sulfides with different phases in aqueous solutions

There is a growing interest in the synthesis of nanostructured copper sulfides due to their ability to form compounds with various stoichiometries. We report a sonochemical route for the preparation of copper sulfides with different compositions in aqueous solutions, using different, general and convenient copper sources such as copper acetate, copper hydroxide or basic copper carbonate and thiourea or thioacetamide as sulfur precursors under ambient air. Phase analysis, purity and morphology of the products were studied by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results revealed that nanoparticles of covellite, CuS, with crystallite sizes between 7 and 18nm can be obtained by using different precursors and complexing agents and that chalcocite, Cu2S, can also be prepared sonochemically.

Single-Source Molecular Precursor for Synthesis of Copper Sulfide Nanostructures

As a new precursor, [bis(thiosemicarbazide)copper(II)]chloride; ([Cu(TSC)2]Cl2), complex was used in thermal decomposition process for the synthesis of Cu2S nanocrystals. The steric hindrance of the precursor raises the need of using co-surfactant, therefore oleylamine (C18H37N) and triphenylphosphine (C18H15P) were applied as solvent and surfactant of the reaction. CuS nanocrystals were synthesized via hydrothermal decomposition of [bis(thiosemicarbazide) copper(II)] without any surfactant. The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and photoluminescence spectroscopy. Synthesized copper sulfide nanostructures have average size of 20–50 nm. Finally, optical properties of the products were examined and investigated by PL spectra.

3D Flowerlike Copper Sulfide Nanostructures Synthesized from Copper (I) Oxide Hollow Microspheres

In the present work, 3D flowerlike CuS nanostructures were synthesized via a facile hydrothermal process using Cu2O hollow microspheres as templates. Reaction of Cu2O hollow microspheres with thioacetamide at 40°C for 2h followed by hydrothermal treatment at 120°C for 12h resulted in high yield of 3D flowerlike structure with diameters ranging from 200 to 300nm. The Influence of experimental parameters on the morphology of the CuS nanostructures was investigated in detail. Different stages of the formation process were studied and thus the formation mechanism of the 3D flowerlike CuS nanostructures was presented.

Synthesis and reaction temperature-tailored self-assembly of copper sulfide nanoplates

Nanostructured copper sulfides have attracted much attention due to their unique electronic and optical properties and potential applications in many areas. This article presents a high-temperature precursor-injection method to synthesize covellite copper sulfide (CuS) nanoplates by using oleylamine as capping ligands. The synthesized CuS nanoplates were found to be self-assembled into face-to-face one-dimensional columnar arrays with the longest column of 0.75 μm. Further studies showed that the reaction temperature has strong effects on the size, size distribution and the self-assembly behaviors of the CuS nanoplates. The self-assembly behaviors were found to be tuned by the reaction temperature. In the range of 140–180 °C, the face-to-face self-assembly is formed over the entire substrate, whereas only edge-to-edge arrangements were observed at the reaction temperature of 200 °C. As the temperature further increases, the product exhibits a mixture of large and small nanocrystals and there is not any presence of self-assembly. The present study highlights the size-controlled synthesis of copper sulfide nanoplates and their self-assembly behaviors dependent on reaction temperature.

New routes to copper sulfide nanostructures and thin films

The copper(II) complex of 1,1,5,5-tetra-iso-propyl-2-thiobiuret [Cu(SON(CNiPr2)2)2], has been synthesized and its single crystal X-ray structure determined. The complex has been used as a single source precursor for the preparation of copper sulfide nanoparticles by solution thermolysis. The nanoparticles synthesized had various morphologies including spherical, hexagonal disks, and trigonal crystallites; depending on the reaction temperature, concentration of the precursor and the growth time. Thermolysis experiments in oleylamine produced Cu7S4 nanoparticles as a mixture of roxbyite (monoclinic) and anilite (orthorhombic) phases. Pure anilite Cu7S4 nanoparticles were obtained when a solution of precursor in octadecene was injected into hot oleylamine whereas, djurleite Cu1.94S nanoparticles were obtained when a solution of the precursor in oleylamine was injected into hot dodecanethiol. The optical properties of the pure anilite Cu7S4 phase and the djurleite Cu1.94S are consistent with indirect band gap materials. The complex was also used for the preparation of copper sulfide thin films by aerosol assisted chemical vapour deposition (AACVD). Powder X-ray diffraction (p-XRD) patterns of the thin films showed the deposition of a mixture of cubic CuS2 and hexagonal Cu2S phases at all temperatures. Scanning Electron Microscopy (SEM) of copper sulfide films showed spherical crystallites from reaction at 280 °C, cuboids at 320 °C and plate like crystallites between 360 and 400 °C. Transmission Electron Microscopy (TEM) of material scratched from thin films showed nanoplates of copper sulfides with 25–30 nm in width.