Effect of Cr-doping on the structural and optical properties of CdS nanoparticles prepared by chemical precipitation method

Undoped and Cr doped CdS nanoparticles have been prepared by chemical precipitation method. X-ray diffraction analysis reveals that the undoped and Cr doped CdS nanoparticles exhibit hexagonal structure and the average particle size of the nanoparticles is in the range of 2.2–3.8 nm. The HRTEM studies show that the average particle size of undoped and Cr doped CdS nanoparticles is in the range of 2–3.7 nm. The compositional analysis results indicates that Cd, S and Cr are present in the samples. From the optical studies it is observed that the absorption edge of the prepared CdS and Cr doped CdS nanoparticles are shifted towards the shorter wavelength region (blue shift) when compared to that of bulk CdS and this shift is due to the quantum confinement effect present in the samples.     

Quantum confinement effects in Gd-doped CdS nanoparticles prepared by chemical precipitation technique

CdS and Gd-doped CdS nanoparticles have been synthesized by chemical precipitation technique. The X-ray diffraction patterns show that the CdS and Gd-doped CdS nanoparticles exhibit hexagonal structure. The high resolution transmission electron microscope image shows that CdS and Gd-doped CdS nanoparticles have particle size lying in the range of 3.5 to 4.0 nm. Raman spectra show that 1LO, 2LO and 3LO peaks of the Gd-doped CdS nanoparticles are slightly shifted to lower wavenumber side when compared to that of CdS. Optical absorption spectra of Gd-doped CdS nanoparticles shows that absorption edge is slightly shifted towards longer wavelength side (red shift) when compared to that of CdS and this shift is due to the quantum confinement effect present in the samples.     

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.     

Strong quantum confinement effect in nanocrystalline CdS

CdS quantum dots have been prepared by chemical method. The X-ray diffraction results indicated the formation of CdS nanoparticles with hexagonal phase and grain size 2.5 nm. The HRTEM analysis reveals the formation of CdS quantum dots with an average grain size of ~2.5 nm. The X-ray photoelectron spectroscopy spectra exhibit the 3d _5/2 and 3d _3/2 peaks corresponding to cadmium and the S2p _3/2 peak corresponding to sulphur. Optical studies by UV–vis spectroscopy show a blue shifted absorption at 471 nm because of the quantum confined excitonic absorption. The photoluminescence spectra of CdS exhibited a broad green emission band centred at around 494 nm.     

Composition dependent structural,Raman and nonlinear optical properties of PVA capped Zn1-x-yCdxCuyS quantum dots

Composition dependent structural, optical nonlinear and limiting properties of PVA capped Zn_1-x-yCd_xCu_yS quantum dots at different Cu:Zn ratio synthesized by insitu technique is subjected to detailed investigation. Cubic phase of the quantum dots were identified from XRD with particle size in the range 2.5 nm–3.5 nm find excellent correlation with the particle size measured from TEM. With increase in Cu concentration: systematic increment in lattice parameter, red shift in absorption edges and luminescence quenching is observed. Raman scattering reveals good photoactivity evidenced by intensity variation and shifting of LO and TO phonon modes. The intensity dependent third order nonlinearity is studied using Q switched Nd: YAG laser with 532 nm irradiation. Progressive increase in 3 PA coefficient indicated that prepared samples exhibit good nonlinear and optical limiting properties.     

Synthesis,structural and optical characterization of Ni-doped ZnO nanoparticles

Nanocrystalline Zn_1−x Ni _x O (x = 0.00, 0.02, 0.04, 0.06, 0.08) powders were synthesized by a simple sol–gel autocombustion method using metal nitrates of zinc, nickel and glycine. Structural and optical properties of the Ni-doped ZnO samples annealed at 800 °C are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis using X-rays (EDAX), UV–visible spectroscopy and photoluminescence (PL). X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a hexagonal wurtzite structure and secondary phase (NiO) was observed with the sensitivity of XRD measurement with the increasing nickel concentration (x ≥ 0.04). The lattice constants of Ni-doped ZnO nanoparticles increase slightly when Ni²⁺ is doped into ZnO lattice. The optical absorption band edge of the nickel doped samples was observed above 387 nm (3.20 eV) along with well-defined absorbance peaks at around 439 (2.82 eV), 615(2.01 eV) and 655 nm (1.89 eV). PL measurements of Ni-doped samples illustrated the strong UV emission band at ~3.02 eV, weak blue emission bands at 2.82 and 2.75 eV, and a strong green emission band at 2.26 eV. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

Chemical synthesis, structural and optical properties of quantum sized semiconducting tin(II) selenide in thin film form

A chemical route to nanocrystalline photoconducting tin(II) selenide quantum dots in thin film form was developed and the structural and optical properties of the synthesized materials were studied. The synthesized SnSe nanocrystals deposited as thin films belong to the orthorhombic crystalline system. Unit cell parameters of the as-deposited and thermally treated semiconducting quantum dots in thin film form were determined from experimental X-ray diffraction data employing multiple regression analysis technique. An average crystal size of 14.8 nm was estimated for as-deposited SnSe quantum dots using the Debye-Scherrer approach which increases to 23.3 nm upon annealing. Average crystal size increase upon thermal treatment is accompanied by slight enlargement of the unit cell parameters. On the basis of optical absorption studies of the SnSe films, conclusions regarding the band structure of this material in reciprocal space were derived. The as-deposited films are characterized by indirect band gap energy of 1.20 eV which exhibits a slight red shift to 1.10 eV upon annealing. Additional electronic transition of a direct type was found to occur at 1.74 eV in the case of as-deposited films, shifting to 1.65 eV in the course of annealing. All these values are blue-shifted with respect to the macrocrystalline material ones, which along with the red shift detected upon annealing, is a strong indication of the three-dimensional confinement effects in the studied nanocrystals.     

Size tuning of MAA capped CdSe and CdSe/CdS quantum dots and their stability in different pH environments

The present work reports synthesis of mercaptoacetic acid capped CdSe nanoparticles soluble in water at different temperatures and with different precursor ratios. This enabled to tune the particle size of QDs from 2.7 to 5.8 nm. The particles consist of nanocrystals; with mixed phase, hexagonal wurtzite as well as sphalerite cubic and are luminescent with quantum yield 10%. The quantum yield up to 20% has been obtained by growing a shell of CdS over the CdSe. HR-TEM images, XRD patterns and the photoluminescence excitation spectra shows epitaxial growth of CdS shell over CdSe and with average size 3.2 ± 1.2 and 4.7 ± 1.2 nm for CdSe and CdSe/CdS quantum dots respectively. FT-IR spectrum and the negative zeta potential value together confirms the attachment of mercaptoacetic acid to the QD surface, where the carboxylic acid group is facing towards solvent and provides stability due to electrostatic hindrance. Further, the QDs are checked for their stability and the luminescence in environments of different pH (4–11 pH). Both CdSe and CdSe/CdS agglomerate with total elimination of fluorescence for 4 pH medium, and no shift in the fluorescence emission peak observed for the 6–9 pH, therefore QDs can be applicable as the fluorescence tags in this specific range of pH.     

Surfactant mediated optical properties of cytosine capped CdSe quantum dots

This letter demonstrates the use of one of the nucleobases, ‘cytosine’ as a new capping agent in controlling the size of the nanoparticles. A size dependent blue shift in optical absorption with enhanced luminescence is observed. Since the calculated density of states do not show any change in the band gap of as-prepared quantum dots after capping, the observed blue shift of the absorption peak can solely be attributed to the so-called size-effect whereas the enhancement in luminescence to surfactant mediated defect passivation. It is expected that the observed properties of the cytosine capped CdSe quantum dots would facilitate a better bio-compatibility of tailor-made nanoparticles for bio-imaging applications.     

Quantum confinement effect of CdS nanoparticles dispersed within PVP/PVA nanocomposites

Nanocomposite films of CdS nanoparticles within PVP/PVA blend were prepared. The prepared films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, Ultraviolet–visible spectroscopy (UV–vis), transmission electron microscopy (TEM) and photoluminescence (PL) spectra. The amount of Cd⁺ used strongly influenced the size of the CdS nanoparticles, which was confirmed by XRD, UV–vis absorption spectra, PL emission spectra and TEM images. Smaller sized CdS nanoparticles were formed in higher content of cadmium. The results of XRD indicate that CdS nanoparticles were formed with hexagonal phase in the polymeric matrix. PL and UV–vis spectra reveal that nanocomposite films shows quantum confinement effect. Optical band gap and particle size were calculated and is in agreement with the results obtained from TEM data. The direct energy band gap was increased up to 2.86 eV.     

Electric field assisted growth of self-organized CdS films: size dependent structural and optical properties

This paper presents a systematic study of electric field assisted growth of self-organized cadmium sulphide (CdS) quantum dots (Q-CdS). CdS thin films of self-organized quantum dot like structure with different particle size have been successfully deposited simply by varying the concentration of surfactant in the reaction matrix. The model to describe the self-organization is also discussed. The size of CdS nanoparticles can be altered from 68 nm (corresponding to bulk) to 2 nm. The structural, optical, and morphological properties of Q-CdS films have been investigated. A blue shift has been observed in optical absorption and photoluminescence spectra. The strained growth of Q-CdS films has been observed. The microstructural strain calculated from peak broadening reveals an increase in strain with decreasing particle size. This study may provide a convenient method to deposit size selective and organized nanocrystalline semiconductor thin films.     

Ferromagnetic and weak superparamagnetic like behavior of Ni-doped ZnS nanocrystals synthesized by reflux method

In this report we have studied the magnetism induced in the undoped and Ni-doped ZnS nanocrystals synthesized via low temperature reflux method. The average diameter of the undoped and Ni-doped nanoparticles is ~3 nm as revealed from transmission electron microscopy and X-ray diffraction (XRD) studies. From XRD studies, the structure of Ni-doped nanocrystals was observed as cubic zinc blende with lattice parameter, a = 0.539 nm. The band gap of the undoped and Ni-doped ZnS nanocrystals, analyzed with UV–visible spectroscopy, was found to be blue shifted as compared to the bulk counterpart. Quenching in photoluminescence spectra was observed at higher Ni concentrations as compared to undoped counterpart. The induced magnetization as analyzed from vibrating samples magnetometer indicated a weak superparamagnetic like behavior in 1 % Ni-doped ZnS nanocrystals, whereas; at 5 and 10 % Ni-doping concentrations, ferromagnetic behavior is indicated.     

Chemical synthesis of CdS nanoparticles and their optical and dielectric studies

Cadmium sulphide nanoparticles were synthesized by chemical displacement reaction method using cadmium nitrate as cadmium source and ammonium sulphide as sulphur source. The CdS samples are characterized using X-ray diffraction, UV–Vis spectroscopy, FTIR spectroscopy, scanning electron microscopy and impedance spectroscopy. CdS nanoparticles are found to possess cubic structure with the crystallite size ~10 nm. The absorption spectra of synthesized CdS nanoparticles revealed the blue shift in excitonic transitions with respect to CdS bulk material, clearly confirming the formation of nanoparticles. The dielectric properties of CdS nanoparticles are studied in the frequency range 10³–10⁷ Hz at room temperature. The dielectric properties of CdS nanoparticles are found to be significantly enhanced specially in the low frequency range due to confinement.     

3-component low temperature solvothermal synthesis of colloidal cadmium sulfide quantum dots

We report the solvothermal synthesis of colloidal cadmium sulfide quantum dots via a three-component system affording various particle diameter ranging from 3.368 nm to 8.411 nm. The band gap, and therefore the optical property, of these nanocrystals can be tuned by varying the reaction time and temperature of the system. The results obtained show strong confinement of particles with diameter smaller than the exciton Bohr radius of CdS. The growth kinetics was found to follow a diffusion-controlled process at the initial stage then shifts to a surface-controlled incorporation of reactants to the crystallite after the particle size becomes comparable to the exciton Bohr radius.     

Synthesis, structural and optical properties of Ni-doped ZnO micro-spheres

Ni doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Ni:Zn atomic ratio from 0 to 5 %. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and nickel acetate tetrahydrate followed by heat treatment at 65 °C under refluxing using methanol as a solvent. X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a wurtzite structure with crystal size of 4–11 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 600–170 nm. High resolution transmission electron microscopy image shows that each sphere is made up of numerous nanoparticles of average diameter 4 nm. The XRD patterns, Scanning electron microscopy and transmission electron microscopy micrographs of doping of Ni in ZnO are confirmed the formation of micro-spheres. Furthermore, the UV–vis. spectra and photoluminescence spectra of the Ni-doped ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.55–3.36 eV by the use of the dopants. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

Photoluminescent properties of ZnS:Mn nanoparticles with in-built surfactant

Mn-doped ZnS nanoparticles, having average diameter 3–5 nm, have been synthesized using chemical precipitation technique without using any external capping agent. Zinc blende crystal structure has been confirmed using the X-ray diffraction studies. The effect of various concentrations of Mn doping on the photoluminescent properties of ZnS nanoparticles has been studied. The time-resolved photoluminescence spectra of the ZnS:Mn quantum dots have been recorded and various parameters like lifetimes, trap depths, and decay constant have been calculated from the decay curves at room temperature. The band gap was calculated using UV–Visible absorption spectra.     

Preparation and optical study of CdS nanocrystals embedded phosphate glass

A new phosphate glass system with CdS nanocrystals dispersed in glass matrix was investigated. The phosphate glass composition with good stability has been used for preparation of CdS doped glasses. The CdS in the range of 0.5-7.0% has been doped into this glass composition. Effect of CdS content on the optical and other properties has been investigated. The optical characterization of the glass samples showed that with increasing concentration of CdS, there was a red shift in transmission cut-off of the glasses. From the transmission cut-off of each glass sample, the band gap of the CdS nanocrystals embedded glass was calculated. The band gap of CdS particles embedded glass was observed in the range of 3.1-4.1 eV. The present system is compared with CdS nanocrystals doped in silica based glass system. In the phosphate glass system, the UV transmission cut-off's are not sharp and the optical transmittance decreases with increasing CdS content in contrast to silica glass system. The reason for such behavior has been discussed in the present investigation. TEM of the CdS doped phosphate glasses showed CdS particle size in the range of 5-7 nm for lower concentration of CdS and 10-100 nm for higher concentration of CdS. The nanocrystals are non-uniform in size but uniformly dispersed in glass matrix.     

Novel nano-structured glasses containing semiconductor quantum dots: controlling the photoluminescence with phonons and photons

Effects of temperatures and excitation intensities on the photoluminescence properties of PbS quantum dots precipitated in the glass were investigated. Peak wavelength of the near-infrared photoluminescence shifted towards the short wavelength side with an increase in temperature and excitation intensity. The largest shift in the peak wavelength of the photoluminescence bands was approximately 90 nm. The temperature coefficient of band gap energy (deduced from the photoluminescence wavelength) of quantum dots varied from 230 to 28 μeV/K under the excitation intensity of 50–600 mW. The integrated photoluminescence intensity also showed similar dependencies on temperature and excitation intensity. The shifts of the photoluminescence with changes in the temperature and excitation intensity were associated with the trapping and re-activation of charge carriers at defect sites located at the QDs/glass interface and inside the glass matrix.     

Influence of the Cd/S Molar Ratio on the Optical and Structural Properties of Nanocrystalline CdS Thin Films

Nanocrystalline CdS thin films have been deposited using precursors with different thiourea concentrationonto glass substrates by sol-gel spin coating method.The crystalline nature of the films has been observedto be strongly dependent on thiourea concentration and annealing temperature.The CdS films are found tobe nanocrystalline in nature with hexagonal structure.The grain size is found to be in the range of 7.6 to11.5 nm depending on the thiourea concentration and annealing temperature.The high resolution transmissionelectron microscopy (HRTEM) results of the CdS films prepared using cadmium to thiourea molar ratio of0.3:0.3 indicate the formation of nanocrystalline CdS with grain size of 5 nm.Fourier transform infrared (FTIR)analysis shows the absorption bands corresponding to Cd and S.The optical study carried out to determinethe band gap of the nanostructured CdS thin films shows a strong blue shift.The band gap energy has beenobserved to lie in the range of 3.97 to 3.62 eV following closely the quantum confinement dependence ofenergy on crystallite radius.The dependence of band gap of the CdS films on the annealing temperature andthiourea concentration has also been studied.The photoluminescence (PL) spectra display two main emissionpeaks corresponding to the blue and green emissions of CdS.     

Effect of 8 MeV electron beam irradiation on the structural and optical properties of CeO2 nanoparticles

The effect of 8 MeV electron beam irradiation on the structural and optical properties of cerium oxide nanoparticles was investigated. Ceria nanoparticles were synthesized by chemical precipitation method, and characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible, photoluminescence and Raman spectroscopy. Ultraviolet–visible absorption spectra, photoluminescence and Raman spectra of beam irradiated samples were modified, and shifted to blue region, which were attributed to quantum size effect. Systematic observations found that nonstoichiometry, defects and size reduction caused by beam irradiation have great influence on optical band gap, blue shift, photoluminescence and Raman band modifications. Moreover, electron beam irradiation is a suitable technique to enhance the structural and optical properties of nanoceria by controlling the particle size, which may lead to potentially useful technological applications.