Optical properties of water-soluble Co:ZnS semiconductor nanocrystals synthesized by a hydrothermal process

Water-soluble ZnS:Co²⁺ nanocrystals (NCs) were synthesized by a low temperature hydrothermal process using 3-mercaptopropionic acid (MPA) as capping agent and the influence of doping on the optical properties of ZnS:Co²⁺ NCs was investigated. It was found that the ZnS:Co²⁺ NCs are highly crystalline and show zinc blende structure with an average particle size of about 7 nm. The lattice constant of the ZnS:Co²⁺ NCs decreases slightly by the introduction of Co²⁺. The Co dopants were well doped into the ZnS:Co²⁺ NCs, as confirmed by X-ray photoelectron spectroscopy(XPS) and the ⁴A₂(F) → ⁴T₁(P) transition of Co²⁺ was detected from the UV-vis absorption spectra. The absorption edge of the ZnS:Co²⁺ NCs is blue-shifted as compared with that of bulk ZnS, indicating the quantum confinement effect. The PL intensity of the NCs shows the maximum value when the Fe-doping concentration is 0.5 at.%.     

Characterization of mono- and multilayered films with Mn-doped ZnS nanoparticles and luminescence properties of the monolayered films prepared by applying magnetic fields

Mn²⁺-doped ZnS (ZnS:Mn) nanoparticles were prepared using bis(2-ethylhexyl) sulfosuccinate (AOT) reversed micelle method. Luminescence at 583-589 nm were observed in the ZnS:Mn nanoparticles and are ascribed to Mn²⁺ ion in the nanoparticles due to energy transfer from ZnS. The luminescence was enhanced by capping with alkanethiol. Mono-and multilayered films with the alkanethiol-capped ZnS:Mn nanoparticles were fabricated on quartz substrates by layer-by-layer method using self-assembled monolayer (SAM) of 1,6-hexanedithiol. The polarization degrees of luminescence for the monolayered films were enhanced by preparation under applying magnetic field. The enhancements are probably caused by magnetic orientation of the ZnS:Mn nanoparticles on the quartz substrates.     

Presence of intrinsic defects and transition from diamagnetic to ferromagnetic state in Co<Superscript>2+</Superscript> ions doped ZnO nanoparticles

In this paper, we report the structural, morphological and magnetic properties of pure and Co²⁺ doped ZnO nanoparticles synthesized using sol–gel auto combustion method. The prepared nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area diffraction pattern (SAED), Fourier transform infrared spectroscopy (FTIR) and photoluminescence spectroscopy. The analysis of XRD pattern shows the single phase nature with a hexagonal wurtzite structure for the prepared nanoparticles. The average crystallite sizes of the prepared nanoparticles were found in the range 18–19 nm. SEM images showed that pure and Co²⁺ doped nanoparticles have different morphology. The shape of the prepared nanoparticles is approximately hexagonal shown by TEM image. SAED pattern also confirms the wurtzite structure with single crystalline nature. FTIR spectra showed the characteristic vibrations frequency band of Zn–O. Photo luminescence spectrum showed that two emission peaks, which are ascribed to near band edge transitions and broadened intensive green emission associated with oxygen-vacancy defects. The magnetic properties were measured by vibrating sample magnetometer (VSM) and superconducting quantum interference device with field dependant magnetization at 300 K and temperature dependant magnetization from 0 to 300 K. From VSM analysis, pure ZnO nanoparticles show diamagnetic behavior while Co²⁺ doped ZnO nanoparticles revealed ferromagnetic behaviour at room temperature. The significant changes in M–H loop from diamagnetic behavior to ferromagnetic behavior are due to the intrinsic defects such as oxygen vacancies (Vo) and zinc vacancies (Vz_n). The RTFM has been presented in terms of vacancies in the frame of bound magnetic polaron model.     

Synthesis and kinetics research of ZnS nanoparticles prepared by sonochemical process

Abstract

ZnS nanocrystallites have been successfully prepared by a sonochemical process. The reaction kinetics of the process was also investigated. The as prepared ZnS nanocrystallites were characterised by XRD and TEM. Results show that ZnS nanoparticles can be obtained by sonochemical process using ZnCl₂ and thiacetamide as raw materials. It is found that the as prepared ZnS nanoparticles are hexagonal phase with spherical or spherical-like morphologies. The grain size decreases with increasing ultrasonic irradiation power. Reaction kinetics shows that the weight content of ZnS nanoparticles increases linearly with reaction time at different temperatures. The synthesis activation energy of ZnS nanoparticles is calculated to be 27·80 kJ mol^–1.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles

ZnS quantum dots of size 3 nm are prepared at 303 K using ZnSO₄ and Na₂S₂O₃ precursors with thioglycerol as stabilizing agent. Cd²⁺ doped ZnS were prepared by varying doping concentration from 1 to 8 wt.%. ZnS quantum dots were mixed with CdS quantum dots of size 4 nm in the 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 M ratio. The nanoparticles were characterized by UV–vis, photoluminescence (PL), XRD and high-resolution TEM measurements. The XRD pattern, high-resolution TEM image and SAED pattern reveal that the nanoparticles are in well-crystallized cubic phase. The band gap of ZnS has increased from the bulk value 3.7 to 4.11 eV showing quantum size effect. Excitonic transition is observed at 274 nm in UV absorption and PL emission at 411 nm. Doping with Cd²⁺ red-shifts both UV and PL spectral bands and enhances the PL band of ZnS nanoparticles. Mixing CdS and ZnS quantum dots in different molar ratios shows red-shift of the band edge in the CdS/ZnS hybrid system. In the 1:1 hybrid system of CdS/ZnS nanoparticles, PL band is red-shifted and the intensity is almost doubled with respect to that of CdS nanoparticles.     

Synthesis of wurtzite ZnS nanocrystals at low temperature

Nanocrystallites of wurtzite hexagonal ZnS have been successfully synthesized without using any capping agent by simple chemical precipitation method at a low calcination temperature of 150 °C. It has been found that the size of the synthesized ZnS nanocrystallites decreases as Zn²⁺:S^2? ratio is decreased. The synthesized nanoparticles have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis absorption spectroscopy and M–H characteristics. The XRD patterns have confirmed that the prepared ZnS nanoparticles are of wurtzite hexagonal phase. XRD, SEM and TEM studies have shown the decrease in the particle size with the increase in S^2? source. TEM images have clearly shown that size distribution of the particles lie in the range of 5–30 nm. The optical absorption bandgap of the synthesized nanocrystals has been found to be in the range of 3.69–3.74 eV. Magnetization study has shown the ‘diamagnetic’ behavior of synthesized ZnS nanocrystallites with a weak ferromagnetic behavior in the low field regime. The observed weak ferromagnetism has been understood due to the presence of defects in the synthesized ZnS nanoparticles.     

Nanostructured thin layers of vanadium oxides doped with cobalt,prepared by pulsed laser ablation: chemistry,local atomic structure,morphology and magnetism

Cobalt-doped vanadium oxide thin layers prepared by pulsed laser ablation are investigated from the following points of view: (1) the chemical states by X-ray photoelectron spectroscopy (XPS), (2) the local atomic order by X-ray absorption fine structure at both vanadium and cobalt K-edges, (3) the morphology of the films by atomic force microscopy (AFM) and (4) the magnetic properties by magneto-optical Kerr effect (MOKE). The chemical composition of the host matrix was found to be close to VO₂ at the sample surface, with V₂O₃ in the bulk. Co ions are found near the surface in high ionisation states Co⁴⁺ (for the samples synthesised in a high vacuum condition, denoted by VO1), or with Co^{(4? δ )+} (for the samples synthesised in an oxygen atmosphere, denoted by VO2), whereas in the bulk, Co^1.5+ is obtained for VO1 and Co²⁺ is obtained for VO2. The AFM revealed nanoparticles with sizes 10–25?nm for VO1 samples, whereas a few bigger nanoparticles are observed for VO2 samples. The VO1 samples presented high coercitive fields with a relatively low saturation magnetisation at room temperature, superposed with a superparamagnetic component attributed to the observed nanoparticles, whereas the VO2 samples presented double-loop hysteresis curves, indicating the co-existence of two kinds of magnetic moieties with antiparallel coupling at zero applied field. The proposed two magnetic phases are Co-doped V₂O₃ and VO₂.     

A high performance cobalt-doped ZnO visible light photocatalyst and its photogenerated charge transfer properties

Highly photocatalytically active cobalt-doped ZnO (ZnO:Co) nanorods have been prepared by a facile hydrothermal process. X-ray diffraction, X-ray photoelectron spectroscopy, Raman scattering and UV-vis diffuse reflectance spectroscopy confirmed that the dopant ions substitute for some of the lattice zinc ions, and furthermore, that Co²⁺ and Co³⁺ ions coexist. The as-prepared ZnO:Co samples have an extended light absorption range compared with pure ZnO and showed highly efficient photocatalytic activity, only requiring 60 min to decompose ∼93% of alizarin red dye under visible light irradiation (λ > 420 nm). The photophysical mechanism of the visible photocatalytic activity was investigated with the help of surface photovoltage spectroscopy. The results indicated that a strong electronic interaction between the Co and ZnO was present, and that the incorporation of Co promoted the charge separation and enhanced the charge transfer ability and, at the same time, effectively inhibited the recombination of photogenerated charge carriers in ZnO, resulting in high visible light photocatalytic activity.      

Paramagnetic nature of Mn doped ZnS nano particles in opto electronic device application

Manganese (Mn²⁺) doped ZnS nano sized powder was prepared by co precipitation method with different concentration from 1 to 5 %. The X-ray diffraction pattern indicates that the prepared powders are in cubic structure with the crystallite sizes lie in the range of 10–12 nm. Diffuse reflectance studies enlightens that an increment in the band gap (3.38–3.55 eV) with increasing dopant. The morphology and size of the sample could be intuitively determined by field emission scanning electron microscope and it shows that ZnS and Mn doped ZnS nanoparticles are appeared as spherical shape. The replacement of Zn by Mn is confirmed by energy dispersive analysis. TEM images confirm the spherical shape of the nanoparticles and SAED images exhibit the crystalline nature and confirm the cubic nature of the synthesized samples. The prepared luminescent nanoparticles of Mn doped ZnS have emission peak at around 617 nm. The symmetry and electronic structure of the Mn doped samples are studied with electron paramagnetic resonance.The paramagnetic nature of Mn doped ZnS nano particles are validated by using vibrating sample magnetometer spectra at room temperature. Thermal analysis measurement of the samples shows that the thermal stability of Mn doped ZnS is higher than the undoped ZnS. This corroborates that ZnS:Mn doping is attributed to the removal of water and it enhanced the crystallinity.     

Sensing of oxidizing and reducing gases by sensors prepared using nanoscale Co3O4 powders: A study through Cu substitution

We demonstrate the sensing-mechanism of both oxidising and reducing gases by nanoscale Co₃O₄ powders through a strategy of Cu-doping in Co₃O₄. The sensitivity towards both types of gases arises due to presence of Co²⁺ and Co³⁺ cations in the (nearly) normal spinel structure of Co₃O₄. Pellets made up of nanopowders were employed for the detection of ～6.5 ppm CO gas present in either pure N₂ or in a mixture of synthetic air as carrier gas (which represents the O₂ sensing-gas too). The high sensitivity of Co₃O₄ nanoparticles to detect ～6 ppm CO (in N₂) arises due to the high surface area of nanopowders exposing a higher number of octahedral Co³⁺ cations as adsorption sites, whereas the sensitivity towards O₂ arises due to partial presence (less number) of octahedral Co²⁺. To support this mechanism, octahedrally Cu²⁺ substituted Co₃O₄ specimens are investigated. The inactive Cu²⁺ at the octahedral site changes the unexposed tetrahedral Co²⁺ into Co³⁺. The presence of inactive Cu²⁺ at the octahedral site and the burial of the Co³⁺ at the tetrahedral sites reduce the adsorption sites for O₂, thereby drastically reducing the overall O₂-gas sensitivity shown by the Cu-substituted sample, although they have higher surface-area (nanoparticles).     

DRIP-XII Conference 2007

Mn²⁺-doped ZnS nanoparticles were synthesized by a hydrothermal method. The reactive conditions are researched, such as the ratios of the reaction concentrations [S²⁻]/[Zn²⁺], the concentration of Mn²⁺ ions, the reaction temperatures and the pH value. The concentration doped-Mn is from 1 mol% to 20 mol% and the hydrothermal synthesis temperatures are from 70 °C to 110 °C. The structure and luminescent properties of ZnS:Mn nanoparticles are researched by using XRD, SEM and PL.     

Structural and luminescence characterization of Eu3+/ZnS nanoparticle-doped ZrO2/PEG composites

ZnS nanoparticles of varying concentrations were incorporated into Eu³⁺ doped ZrO₂/PEG composite system through non-hydrolytic sol–gel method. The presence of the nanoparticles was confirmed by XRD and TEM analyses. The elemental composition of the prepared sample was verified using EDX analysis. Different vibrational modes of the composite system were found out by FTIR spectra. Thermal stability of the as-prepared sample was measured using TGA and DTA analyses. The optical bandgap of the composite system was calculated from the absorption spectrum. The excitation spectrum shows the broad excitation bands of the sensitizer (ZnS) and Host (ZrO₂/PEG) as well as the characteristic excitation peaks of the activator (Eu³⁺). The emission spectra reveal that the characteristic emission of Eu³⁺ can be obtained using 392 nm as well as the excitation wavelength of the sensitizer (275 nm). The CIE chromaticity analysis shows a change in the emission colour of the co-doped samples from yellow to reddish orange corresponding to a change in the excitation wavelength from 392 to 275 nm. These results suggest the applicability of the as-synthesized composite system as a potential candidate in various optoelectronic devices.

     

Core/Shell ZnO/ZnS Nanoparticle Electron Transport Layers Enable Efficient All-Solution-Processed Perovskite Light-Emitting Diodes

Solution-processed perovskite-based light-emitting diodes (PeLEDs) are promising candidates for low-cost, large-area displays, while severe deterioration of the perovskite light-emitting layer occurs during deposition of electron transport layers from solution in an issue. Herein, core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer in PeLED based on quasi-2D PEA₂Cs_n−1Pb_nBr_3n+1 (PEA = phenylethylammonium) perovskite are employed. The deposition of ZnS shell mitigates trap states on ZnO core by anchoring sulfur to oxygen vacancies, and at the same time removes residual hydroxyl groups, which helps to suppress the interfacial trap-assisted non-radiative recombination and the deprotonation reaction between the perovskite layer and ZnO. The core/shell ZnO/ZnS nanoparticles show comparably high electron mobility to pristine ZnO nanoparticles, combined with the reduced energy barrier between the electron transport layer and the perovskite layer, improving the charge injection balance in PeLEDs. As a result, the optimized PeLEDs employing core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer exhibit high peak luminance reaching 32 400 cd m⁻², external quantum efficiency of 10.3%, and 20-fold extended longevity as compared to the devices utilizing ZnO nanoparticles, which represents one of the highest overall performances for solution-processed PeLEDs.     

Tuning photoluminescence of ZnS nanoparticles by silver

We report the results of investigation of the interaction of silver with presynthesized ZnS nanoparticles (NPs) that was stabilized by cetyl trimethyl ammonium bromide (CTAB). The photoluminescence properties of ZnS NPs were followed in the presence of Ag⁺ ions, Ag NPs and by the synthesis of Ag@ZnS core-shell nanoparticles. We observed that CTAB stabilized ZnS NPs emitted broadly in the region from 350–450 nm, when excited by 309 nm light. In the presence of Ag⁺ ions the emission peak intensity up to 400 nm was reduced, while two new and stronger peaks at 430 nm and 550 nm appeared. Similar results were obtained when Ag NPs solution was added to ZnS solution. However, when Ag@ZnS NPs were synthesized, the emission in the 350–450 nm region was much weaker in comparison to that at 540 nm, which itself appeared at a wavelength shorter than that of Ag⁺ ion added ZnS NPs. The observations have been explained by the presence of interstitial sulfur and Zn²⁺, especially near the surface of the nanocrystals and their interaction with various forms of silver. In addition, our observations suggest that Ag⁺ ions diffuse into the lattice of the preformed ZnS NPs just like the formation of Ag⁺ doped ZnS NPs and thus changes the emission characteristics. We also have pursued similar experiments with addition of Mn²⁺ ions to ZnS and observed similar results of emission characteristics of Mn²⁺ doped ZnS NPs. We expect that results would stimulate further research interests in the development of fluoremetric metal ion sensors based on interaction with quantum dots.     

Evidence of Variable Range Hopping (VRH) and Exchange Interaction in Co-Doped Multiferroic BiMnO3 Nanoparticles

Among ABO₃-type oxides, centrosymmetric (C2/c) BiMnO₃ is one of the few single-phase multiferroics, with a highly distorted perovskite structure that has been extensively studied. In this work, to stabilize the crystal structure, to control temperature dependence of electrical properties and to induce low coercivity at low temperature, strategy of doping transition metal has been adopted for useful applications. Well-crystallized single-phase cobalt-doped bismuth manganite nanoparticles having general formula BiCo _x Mn_1?x O₃ (x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized by co-precipitation method. All compositions show that substituting Mn with Co, in BiMnO₃-based compounds enhances better and more stable structural properties, like lattice parameters and crystallite size, phase transition temperatures, temperature-dependent DC electrical properties and magnetic properties. The extrinsic contribution to the temperature-dependent electrical properties is an increased resistivity due to charge localization. The magnetic properties due to transition metal doping are strongly affected by the super-exchange interaction phenomenon between Co³⁺ and Mn⁴⁺ cations.     

Effects of Co content and annealing temperature on the structure and optical properties of CoxMg1−xAl2O4 nanoparticles

Co_xMg_1−xAl₂O₄ (x = 0–0.8) nanoparticles were synthesized by sol–gel method, and characterized by X-ray powder diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy and ²⁷Al solid-state NMR spectroscopy were performed to study the chemical environments of cations in the nanoparticles as a function of cobalt content and annealing temperature. The results show that the crystallite size of the particles is about 20–40 nm. Besides the tetrahedral and octahedral coordinations, the second octahedrally coordinated Al³⁺ ions are observed in the samples. The inversion parameter (two times the fraction of Al³⁺ ions in tetrahedral sites) decreases with the increase of annealing temperature and cobalt content. The fraction of octahedral Mg²⁺ decreases with the increase of Co concentration. The absorption spectra indicate that Co²⁺ ions are located in the tetrahedral sites as well as in the octahedral sites in the nanoparticles. The intensity of the absorption peak corresponding to octahedral Co²⁺ ions (300–500 nm) decreases with increasing annealing temperature.     

Fine particles of lanthanum-and cobalt-doped strontium hexaferrite prepared through glass crystallization

Glass of nominal composition Sr_0.6La_0.4Fe_11.6Co_0.4O₁₉ + 12SrB₂O₄ was prepared by rapidly quenching an oxide melt and was then heat-treated at temperatures from 550 to 900°C to give glass-ceramics containing fine lanthanum-and cobalt-doped strontium hexaferrite particles and microcrystalline SrB₂O₄. The materials were characterized by x-ray diffraction, scanning electron microscopy, electron probe x-ray microanalysis, and magnetic measurements. The coercivity of the glass-ceramic samples was shown to increase up to 427 kA/m with increasing heat-treatment temperature. The saturation magnetization of the samples increases up to 25.0 A m²/kg as the heat-treatment temperature is raised to 750°C, and decreases slightly at higher temperatures. Dissolving the nonmagnetic matrix of the glass-ceramic prepared at 900°C, we obtained submicron powder of composition Sr_0.88La_0.12Fe_10.74Co_0.47O_y, as determined by x-ray microanalysis.     

Adsorption behavior of Co(II) and Ni(II) from aqueous solutions onto titanate nanotubes

Adsorption of Co²⁺ and Ni²⁺ from aqueous solutions onto titanate nanotubes (TNTs) synthesized by hydrothermal method in single and binary systems was investigated. The prepared TNTs were completely characterized showing very high surface area compared to previous studies (320 m²/g). The high surface area showed very good optimum removal conditions compared with previous studies (60 min contact time, 0.1 g TNTs dose at pH 5 and room temperature) with high adsorption capacity compared with previous studies as well as conventional adsorbent. Langmuir and Freundlich isothermal models were fitted during this study and Dubinin–Kaganer–Radushkevich isotherms showed physisorption with exclusion of ion exchange mechanism. Pseudo first and second-order kinetics were studied showing more fitting to pseudo second-order equation. Binary system and calculation of separation coefficient showed high ability for Co²⁺ adsorption by TNTs than Ni⁺² in binary system.     

Template-free hydrothermal derived cobalt oxide nanopowders: Synthesis,characterization, and removal of organic dyes

Pure spinel cobalt oxide nanoparticles were prepared through hydrothermal approach using different counter ions. First, the pure and uniform cobalt carbonate (with particle size of 21.8–29.8 nm) were prepared in high yield (94%) in an autoclave in absence unfriendly organic surfactants or solvents by adjusting different experimental parameters such as: pH, reaction time, temperature, counter ions, and (Co²⁺:CO₃^2?) molar ratios. Thence, the spinel Co₃O₄ (with mean particle size of 30.5–47.35 nm) was produced by thermal decomposition of cobalt carbonate in air at 500 °C for 3 h. The products were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), transmission electron microscope (TEM), scanning electron microscope (SEM), and thermal analysis (TA). Also, the optical characteristics of the as-prepared Co₃O₄ nanoparticles revealed the presence of two band gaps (1.45–1.47, and 1.83–1.93 eV). Additionally, adsorption of methylene blue dye on Co₃O₄ nanoparticles was investigated and the uptake% was found to be >99% in 24 h.     

Optical properties of Mn-doped ZnS semiconductor nanoclusters synthesized by a hydrothermal process

Undoped and Mn-doped ZnS nanoclusters have been synthesized by a hydrothermal approach. Various samples of the ZnS:Mn with 0.5, 1, 3, 10 and 20 at.% Mn dopant have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-ray, high resolution electron microscopy, UV-vis diffusion reflection, photoluminescence (PL) and photoluminescence excitation (PLE) measurements. All the prepared ZnS nanoclusters possess cubic sphalerite crystal structure with lattice constant a = 5.408 ± 0.011 ?. The PL spectra of Mn-doped ZnS nanoclusters at room temperature exhibit both the 495 nm blue defect-related emission and the 587 nm orange Mn²⁺ emission. Furthermore, the blue emission is dominant at low temperatures; meanwhile the orange emission is dominant at room temperature. The Mn²⁺ ion-related PL can be excited both at energies near the band-edge of ZnS host (the UV region) and at energies corresponding to the Mn²⁺ ion own excited states (the visible region). An energy schema for the Mn-doped ZnS nanoclusters is proposed to interpret the photoluminescence behaviour.