Synthesis and optical properties of Cr doped ZnS nanoparticles capped by 2-mercaptoethanol

Nanoparticles of Zn_1−xCr_xS (x=0.00, 0.005, 0.01, 0.02 and 0.03) were prepared by a chemical co-precipitation reaction from homogenous solutions of zinc and chromium salts. These nanoparticles were sterically stabilized using 2-mercaptoethanol. Here a study of the effect of Cr doping on structural, morphological and optical properties of nanoparticles was undertaken. Elemental analysis, morphological, structural and optical properties have been investigated by energy dispersive analysis of X-rays (EDAX), scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible spectroscopy .EDAX measurements confirmed the presence of Cr in the ZnS lattice. XRD showed that ZnS:Cr nanoparticles crystallized in zincblende structure with preferential orientation along (1 1 1) plane. The average sizes of the nanoparticles lay in the range of 3-6 nm and lattice parameters were in the range of 5.2-5.4 Å. Lattice contraction was observed with an increase of Cr concentration. The particle size and lattice parameters obtained from TEM and SAED images were in agreement with the XRD results. The absorption edge shifted to lower wavelengths with an increase in Cr concentration as per UV-Vis spectroscopy. The band gap energy values were in the range of 3.85-4.05 eV. This blueshift is attributed to the quantum confinement effect.     

Effect of impurity concentration on optical and magnetic properties in ZnS:Cu nanoparticles

To obtain enhanced room temperature ferromagnetism (RTFM) along with the increase in optical bandgap in the compound semiconductors has been an interesting topic. Here, we report RTFM along with increase in energy bandgap in chemically synthesized Zn_1−xCu_xS (0 ≤ x ≤ 0.04) DMS nanoparticles. Structural properties of the synthesized samples studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show the formation of cubic phase Cu doped ZnS nanoparticles of ~3–5 nm size. An intrinsic weak ferromagnetic behavior was observed in pure ZnS sample (at 300 K) which got increased in Cu doped samples and was understood due to defect induced ferromagnetism. UV–vis measurement showed increase in the energy bandgap with the increase in Cu doping. The PL study suggested the presence of sulfur and zinc vacancies and surface defects which were understood contributing to the intrinsic FM behavior.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Study of optical and thermal properties in nickel doped ZnS nanoparticles using surfactants

The presence of surfactants polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), sodium hexameta polyphosphate (SHMP) and tri-octyl phosphine oxide (TOPO) on the surface of Ni²⁺ doped ZnS (ZnS:Ni²⁺) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped ZnS:Ni²⁺ nanoparticles were investigated using UV–visible (UV–Vis) absorption and photoluminescence (PL) techniques. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc sulfide. The effect of the optical properties in colloidal form (wet) and dry samples were investigated. Enhanced PL emission was observed for the dry samples at 80 °C. Thermal properties of the ZnS:Ni²⁺ was also studied using thermo gravimetric-differential thermal analysis (TG-DTA), Fourier transform infra-red spectrometer (FT-IR) and X-ray diffraction (XRD). The results are presented and discussed.     

Synthesis,structural, optical,and magnetic properties of Co doped,Sm doped and Co+Sm co-doped ZnS nanoparticles

The compositional, structural, optical and magnetic properties of ZnS, Zn_0.98Co_0.02S, Zn_0.98Sm_0.02S and Zn_0.96Co_0.02Sm_0.02S nanoparticles synthesized by a hydrothermal method are presented and discussed. X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) studies revealed that all the samples exhibited cubic structure without any impurity phases. X-ray photoelectron spectroscopy (XPS) results revealed that the Co and Sm ions existed in +2 and +3 states in these samples. The photoluminescence (PL) spectra of all the samples exhibited a broad emission in the visible region. The room temperature magnetization versus applied magnetic field (M–H) curves demonstrated that the Sm+Co doped nanoparticles exhibited enhanced ferromagnetic behavior compare to Co and Sm individually doped ZnS nanoparticles, which is probably due to the exchange interaction between conductive electrons with local spin polarized electrons on the Co²⁺ or Sm³⁺ ions. This study intensifies the understanding of the novel performances of co-doped ZnS nanoparticles and also provides possibilities to fabricate future spintronic devices.     

Mechano-chemical synthesis and optical properties of ZnS nanoparticles

In the present work, we report the synthesis and optical properties of ZnS nanoparticles produced by the mechano-chemical route. We used zinc acetate and sodium sulphide as source materials in a high energy planetary ball mill at rotation speed of 300 rpm and vial rotation speed of 600 rpm with ball to powder (BPR or charge ratio CR) 5:1 for 30 and 90 min. The milled powders were washed with methanol to remove impurity and dried at 300 °C for 1 h. The prepared nanoparticles have been characterized using X-ray diffraction (XRD), Field emission scanning electron microscope (FESEM), UV–vis–NIR spectrophotometer and Fluorescence spectroscopy. The crystallite size of the synthesized ZnS nanoparticles is found to be in the range 7–8 nm which was calculated using Debye–Scherer's formula. The value of optical band gap has been found to be in the range 3.80–4.15 eV. Room temperature photoluminescence (PL) spectrum of ZnS samples exhibit a blue emission peaked at 466 nm under UV excitation.     

Effect of annealing temperature on structure, magnetic properties and optical characteristics in Zn0.97Cr0.03O nanoparticles

The Cr-doped zinc oxide (Zn_0.97Cr_0.03O) nanoparticles were successfully synthesized by sol-gel method. The relationship between the annealing temperature (400 °C, 450 °C, 500 °C and 600 °C) and the structure, magnetic properties and the optical characteristics of the produced samples was studied. The results indicate that Cr (Cr³⁺) ions at least partially substitute Zn (Zn²⁺) ions successfully. Energy dispersive spectroscopy (EDS) measurement showed the existence of Cr ion in the Cr-doped ZnO. The samples sintered in air under the temperature of 450 °C had single wurtzite ZnO structure with prominent ferromagnetism at room temperature, while in samples sintered in air at 500 °C, a second phase-ZnCr₂O₄ was observed and the samples were not saturated in the field of 10000 Oe. This indicated that they were mixtures of ferromagnetic materials and paramagnetic materials. Compared with the results of the photoluminescence (PL) spectra, it was reasonably concluded that the ferromagnetism observed in the studied samples was originated from the doping of Cr in the lattice of ZnO crystallites.     

Structural and optical properties of Mn doped ZnS semiconductor nanostructures

Manganese doped zinc sulphide nanoparticles were fabricated by adopting an inexpensive solution growth route. Different samples were fabricated by varying Mn concentrations. UV-VIS study reveals blue-shift on the onset of absorption and hence enhancement in the optical band gap upto 0.75 eV, indicating strong quantum confinement. Photoluminescene study for all the samples display characteristic band edge peak at ∼410 nm. The broad peak ∼560–580 nm is ascribed to Mn incorporation. Further, structural investigations were carried out by using X-Ray diffraction and transmission electron microscopy (TEM).     

Facile synthesis and magnetic properties of manganese doped ZnS nanorods

The synthesis of both Mn(II) doped and undoped ZnS nanorods were carried out using a simple soft-chemical route using mercaptoethanol as capping agent. Their morphological, structural and magnetic properties are presented. The crystal structures of the as obtained products were investigated through X-ray diffraction study reveals the formation of hexagonal wurtzite structure. The growth of the nanorods is achieved by careful control over the precursor addition, temperature and time duration. The nanorods are single crystalline and the diameter of the rods was found to vary in the range of 20-50 nm. Vibrating sample magnetometer measurements at room temperature show paramagnetic behavior for the doped nanorods.     

Effect of annealing on structural, optical and electrical properties of ZnS/porous silicon composites

ZnS films were prepared by pulsed laser deposition (PLD) on porous silicon (PS) substrates. This paper investigates the effect of annealing temperature on the structural, morphological, optical and electrical properties of ZnS/PS composites by x-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) and I--V characteristics. It is found that the ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction, and the intensity of diffraction peak increases with increasing annealing temperature, which is attributed to the grain growth and the enhancement of crystallinity of ZnS films. The smooth and uniform surface of the as-prepared ZnS/PS composite becomes rougher through annealing treatment, which is related to grain growth at the higher annealing temperature. With the increase of annealing temperature, the intensity of self-activated luminescence of ZnS increases, while the luminescence intensity of PS decreases, and a new green emission located around 550~nm appeared in the PL spectra of ZnS/PS composites which is ascribed to the defect-center luminescence of ZnS. The I--V characteristics of ZnS/PS heterojunctions exhibited rectifying behavior, and the forward current increases with increasing annealing temperature.     

The influence of annealing temperature on the structure,morphologies and optical properties of ZnO nanoparticles

ZnO nanoparticles (NPs) have been successfully synthesized by the simple solution method at low temperature. The effects of annealing temperature on the structure and optical properties of ZnO NPs were investigated in detail by X-ray diffraction, transmission electron microscopy (TEM), ultraviolet–visible (UV–vis) spectroscopy and photoluminescence (PL) measurements. As the annealing temperature was increased above 180 ^°C the particles morphology evolved from spherical to hexagonal shape, indicating that the average particle size increased from 11 nm to 87 nm. The UV-vis and PL spectra showed a red-shift from 3.62 to 3.33 eV when the annealing temperature was increased.     

Effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles

We explore the effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles synthesized by the sol-gel method. X-ray diffraction and x-ray photoelectron spectroscopy data show evidence that Cr has been incorporated into the wurtzite ZnO lattice as Cr²⁺ ions substituting for Zn²⁺ ions without any detectable secondary phase in as-synthesized Zn_0.97Cr_0.03O nanopowders. The room temperature magnetization measurements reveal a large enhancement of saturation magnetization M_s as well as an increase of coercivity of H₂-annealed Zn_0.97Cr_0.03O:H samples. It is found that the field-cooled magnetization curves as a function of temperature from 40 to 400 K can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H₂-annealed Zn_0.97Cr_0.03O:H nanoparticles are almost doubled upon H₂-annealing. Photoluminescence measurements show evidence that the shallow donor defect or/and defect complexes such as hydrogen occupying an oxygen vacancy H_o may play an important role in the origin of H₂-annealing induced enhancement of ferromagnetism in Cr-H codoped ZnO nanoparticles.     

First principles study on magnetic properties in ZnS doped with palladium

The electronic structures and magnetic properties in zinc-blende structure ZnS doped with nonmagnetic noble metal palladium have been investigated by means of density functional theory (DFT) calculations employing the generalised gradient approximation (GGA) and the GGA plus Hubbard U (GGA + U). Both the GGA and GGA + U methods demonstrate half-metallicity in Pd-doped ZnS with total magnetic moments of about 2.0μ _B per supercell. The half-metallic ferromagnetism stems from the hybridisation between Pd-4d and S-3p states and could be attributed to a double-exchange mechanism. These results suggest a recipe for obtaining a promising dilute magnetic semiconductor by doping nonmagnetic 4d elements in ZnS matrix.     

The effect of annealing temperature on structural and optical properties of undoped and Cu doped CdS thin films

Cadmium sulphide (CdS) thin films were prepared chemical bath deposition technique. The films were doped with copper using the direct method consisting in the addition of a copper salt in the deposition bath of CdS. The doped films were annealed in air, at 250, 300 and 350 °C, for 1 h. The deposition films were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive analysis by X-rays (EDAX) and optical properties of CdS thin films before and after Cu doping. XRD analysis shows that the films are polycrystalline in nature with cubic crystalline structure. The various parameters such as crystallite size, micro strain and dislocation density were evaluated. SEM study shows that the total substrate surface is well covered by uniformly distributed spherical shaped grains. Optical transmittance study shows the presence of direct transition with band gap energy decrease 2.5–2.2 eV.     

Preparation and photoluminescent properties of doped nanoparticles of ZnS by solid-state reaction

Nanometer-sized Eu³⁺-doped ZnS and Mn²⁺-doped ZnS particles were prepared by solid-state method at low temperature. The structures and properties of those materials were characterized by X-ray diffraction (XRD) and photoluminescent spectroscopy techniques. The XRD patterns reveal that the doped ZnS nanoparticles belong to zinc-blende structure. The concentration of doping ions has little effect on the sizes of the doped ZnS nanoparticles, which mainly depends on the temperature of preparation. The emission peaks from the ⁵D₀→⁷F_J (J=1, 2, and 4) electronic energy transitions of Eu³⁺ were observed in the emission spectra of the ZnS:Eu³⁺ nanoparticles. The intensity ratio of the two peaks from the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions indicates that more Eu³⁺ ions occupy the sites with no inversion symmetry. For the ZnS:Mn²⁺ nanoparticles, an orange emission from the ⁴T₁→⁶A₁ transition of Mn²⁺ is present, indicating that the doping ions occupy the positions of the ZnS lattices. Meanwhile, UV-induced luminescence enhancement was observed for the ZnS:Mn²⁺ nanoparticles, the possible reason of which is discussed primarily.     

Effect of annealing on optical and structural properties of ZnS/MnS and MnS/ZnS superlattices thin films for solar energy application

ZnS/MnS super lattice thin films were grown on glass substrates by Chemical Bath Deposition technique. Equimolar aqueous solutions of ZnCl₂:thiourea and MnCl₂·2H₂O:thiourea were taken separately. The substrates were placed vertically in the beakers containing the precursor described above, and the films are deposited at 85 °C for an hour. The as deposited films are annealed at 200 °C for about two hours. X-ray diffractometry method was used to obtain structural characterization. The UV–vis absorption spectrometry was employed to find the optical properties. The refractive-index, dielectric constant, optical conductivity, electrical conductivity and extinction coefficient were determined by various equations based on the data. The valence band and conduction band offset voltages for ZnS/MnS were determined as 0.7 eV and 0.1 eV respectively and for MnS/ZnS were 0.4 eV and 0.3 eV respectively. The band alignment of both superlattice was found to be as Type I.     

Ti和Al共掺杂ZnS的电子结构和光学性质

基于密度泛函理论的第一性原理研究Ti和Al单掺杂和(Ti,Al)共掺杂ZnS的能带结构、电子态密度分布、介电函数、光学吸收系数,分析了掺杂后电子结构与光学性质的变化.计算结果表明:掺杂后禁带中引入了新的杂质能级,费米能级进入导带.掺杂改变了ZnS晶体的导电特性,使它表现出金属特性,导电性能增强;与纯净ZnS相比,Ti单掺杂和(Ti,Al)共掺杂ZnS的吸收边均出现明显的红移,且在1.79eV左右出现了一个新峰;而Al单掺杂ZnS的吸收边则发生明显的蓝移,且不产生新的吸收峰.     

Structural and magnetic properties of Cr and Mn doped InN

We present a detailed magnetic characterization of Cr and Mn doped InN films be means of superconducting quantum interference device magnetometry and X-ray magnetic circular dichroism. The InN:Cr films exhibit ferromagnetic behavior up to 300 K in a doping region from 2% to 8% without detectable phase segregation. The easy axis of magnetization is found to be in the film plane. On the contrary, Mn-doped films show signatures of phase segregation and paramagnetic behavior.     

Effect of thermal annealing on disorder and optical properties of Cr/Si bilayer thin films

Chromium/silicon bilayers are deposited by sequential electron beam evaporation on quartz substrates. The bilayers consisting of Cr and Si layers of 50 and 400 nm thicknesses, respectively, are subjected to post-deposition annealing at temperatures from 200 to 700 °C. The thermal annealing results in the interdiffusion between Cr and Si, as evidenced by cross-section scanning electron micrographs and the line profiles obtained from energy-dispersive X-ray spectroscopy. It is inferred from the compositional line profiles that the films are a combination of silicon-rich oxide, chromium oxide and unreacted Cr up to 500 °C. Chromium disilicide forms at temperatures greater than 500 °C with decrease in chromium oxide content. The refractive index value and extinction coefficient values are 2.1 and 0.12 in the as-deposited case which increase to 3.5 and 0.24 at 400 °C. These values decrease to 2.1 and 0.12 at 500 °C. At the same temperatures, the band gap values are 2.21, 2.40 and 2.28, respectively. Thus, the refractive index, absorption coefficient and the optical band gap of the films peak at an annealing temperature of 400 °C and decrease thereafter. Significantly, this is accompanied by increase in Urbach energy which is an indication of increase in disorder in the system. There is decrease in Urbach energy as well as the optical constants at temperatures >400 °C.     

过渡金属TM(V,Cr,Mn)掺杂ZnS的电子结构和磁性

采用基于密度泛函理论(DFT)的第一性原理赝势平面波方法,对过渡金属V、Cr、Mn掺杂ZnS的超晶胞体系进行了几何结构优化,计算了晶格常数、电子结构与磁学性质.研究结果表明:掺入V,Cr后,ZnS表现出明显的半金属性,而掺入Mn后,半金属性不明显;掺入过渡金属TM(V,Cr,Mn)后系统产生的磁矩主要有杂质的3d态电子贡献,且磁矩的大小与过渡金属的电子排布有关.