Doping dependent room-temperature ferromagnetism and structural properties of dilute magnetic semiconductor ZnO:Cu nanorods

Copper doped ZnO nanoparticles were synthesized by the chemical technique based on the hydrothermal method. The crystallite structure, morphology and size were determined by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) for different doping percentages of Cu²⁺ (1-10%). TEM/SEM images showed formation of uniform nanorods, the aspect ratio of which varied with doping percentage of Cu²⁺. The wurtzite structure of ZnO gradually degrades with the increasing Cu²⁺ doping concentration and an additional CuO associated diffraction peak was observed above 8% of Cu²⁺ doping. The change in magnetic behavior of the nanoparticles of ZnO with varying Cu²⁺ doping concentrations was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong room-temperature ferromagnetic behavior, however at higher doping percentage of copper the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced.     

Synthesis and characterization of Mg-doped ZnO hollow spheres

Mg-doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Mg:Zn atomic ratio from 0 to 7%. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and magnesium acetate tetrahydrate were heated under refluxing at 65 °C using methanol as a solvent. X-ray diffraction analysis reveals that the Mg-doped ZnO crystallizes in a wurtzite structure with crystal size of 5–12 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 800–1100 nm. High resolution transmission electron microscopy images show that each sphere is made up of numerous nanoparticles of average diameter 5–11 nm. The XRD patterns, SEM and TEM micrographs of doping of Mg in ZnO confirmed the formation of hollow spheres indicating that the Mg²⁺ is successfully substituted into the ZnO host structure of the Zn²⁺ site. Furthermore, the UV–Vis spectra and photoluminescence (PL) spectra of the ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.36–3.55 eV by the use of the dopants.     

Synthesis and characterization of Cu doped ZnS nanoparticles using TOPO and SHMP as capping agents

Undoped and Cu²⁺ doped (0.2-0.8%) ZnS nanoparticles have been synthesized through chemical precipitation method. Tri-n-octylphosphine oxide (TOPO) and sodium hexametaphosphate (SHMP) were used as capping agents. The synthesized nanoparticles have been analyzed using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrometer (FT-IR), UV-vis spectrometer, photoluminescence (PL) and thermo gravimetric-differential scanning calorimetry (TG-DTA) analysis. The size of the particles is found to be 4-6 nm range. Photoluminescence spectra were recorded for ZnS:Cu²⁺ under the excitation wavelength of 320 nm. The prepared Cu²⁺-doped sample shows efficient PL emission in 470-525 nm region. The capped ZnS:Cu emission intensity is enhanced than the uncapped particles. The doping ions were identified by electron spin resonance (ESR) spectrometer. The phase changes were observed in different temperatures.     

Effect of barium doping on the physical properties of zinc oxide nanoparticles elaborated via sonochemical synthesis method

The aim of this work is to study the effect of barium (Ba) doping on the optical, morphological and structural properties of ZnO nanoparticles. Undoped and Ba-doped ZnO have been successfully synthesized via sonochemical method using zinc nitrate, hexamethylenetetramine (HMT) and barium chloride as starting materials. The structural characterization by XRD and FTIR shows that ZnO nanoparticles are polycrystalline with a standard hexagonal ZnO wurtzite crystal structure. Decrease in lattice parameters from diffraction data shows the presence of Ba²⁺ in the ZnO crystal lattice. The morphology of the ZnO nanoparticles has been determined by scanning electron microscopy (SEM). Incorporation of Ba was confirmed from the elemental analysis using EDX. Optical analysis depicted that all samples exhibit an average optical transparency over 80%, in the visible range. Room-temperature photoluminescence (PL) spectra detected a strong ultraviolet emission at 330 nm and two weak emission bands were observed near 417 and 560 nm. Raman spectroscopy analysis of Ba-doped samples reveals the successful doping of Ba ions in the host ZnO.     

Optical properties of pyridine funtionalized TbF<Subscript>3</Subscript> nanoparticles

The preparation of pyridine functionalized TbF₃ nanoparticles are described in this report. Synthesized nanoparticles were characterized using the TEM, UV/Vis, FTIR and photoluminescence spectroscopy. TEM micrograph reveals the nanorod shaped, uniform in size with a particles size in the range of 20–30 nm. FTIR spectrum shown characteristic absorption bands of pyridine and a small intensity band at 411 cm⁻¹ corresponding metal nitrogen ν(Tb–N) bonding. Uv-vis spectrum shown the characteristic absorption transitions of Tb³⁺ ion. A strong emission transition at 540 nm (⁵D₄ → ⁷F₅) was observed on excite by visible light at 414 nm.     

Effect of Mn doping on the structural and optical properties of sol-gel derived ZnO nanoparticles

Un-doped and Mn-doped ZnO nanoparticles were successfully synthesized in an ethanolic solution by using a sol-gel method. Material properties of the samples dependence on preparation conditions and Mn concentrations were investigated while other parameters were controlled to ensure reproducibility. It was observed that the structural properties, particle size, band gap, photoluminescence intensity and wavelength of maximum intensity were influenced by the amount of Mn ions present in the precursor. The XRD spectra for ZnO nanoparticles show the entire peaks corresponding to the various planes of wurtzite ZnO, indicating a single phase. The diffraction peaks of doped samples are slightly shifted to lower angles with an increase in the Mn ion concentration, signifying the expansion of the lattice constants and increase in the band gap of ZnO. All the samples show the absorption in the visible region. The absorbance spectra show that the excitonic absorption peak shifts towards the lower wavelength side with the Mn-doped ZnO nanoparticles. The PL spectra of undoped ZnO consist of UV emission at 388 nm and broad visible emission at 560 nm with varying relative peak intensities. The doping of ZnO with Mn quenches significantly the green emission while UV luminescence is slightly affected.     

Synthesis by sol–gel process,structural and optical properties of nanoparticles of zinc oxide doped vanadium

We report the elaboration of vanadium-doped ZnO nanoparticles prepared by a sol–gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at.% has been investigated. After treatment in air at different temperatures, the obtained nanopowder was characterised by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). Analysis by scanning electron microscopy at high resolution shows that the grain size increases with increasing temperature. Thus, in the case of thermal treatment at 500 °C in air, the powder with an average particle size of 25 nm shows a strong luminescence band in the visible range. The intensity and energy position of the obtained PL band depends on the temperature measurement increase. The mechanism of this emission band is discussed.     

Spectrally broadened excitonic absorption and enhanced optical nonlinearities in Dy<Superscript>3+</Superscript>-doped ZnO nanoparticles

We have synthesized Dy³⁺-doped ZnO nanoparticles at room temperature through the sol–gel method. X-ray diffraction and Scanning electron microscopic studies confirm the crystalline nature of the particles. Excitonic absorption of ZnO shows three different bands, and we observe that incorporation of Dy³⁺ results in the shifting and broadening of the n=1 absorption band of ZnO. Photoluminescence studies done at the excitation wavelength of 335 nm show broad emission containing five different bands. Open-aperture z-scan studies done at 532 nm using 5 ns laser pulses show an optical limiting behavior, which numerically fits to a three-photon type absorption process. The nonlinearity is essentially resonant, as it is found to increase consistently with Dy³⁺ concentration. This feature makes Dy³⁺-doped ZnO a flexible optical limiter for potential device applications.     

Enhanced visible light emission from Co doped ZnS nanoparticles

ZnS nanoparticles with Co²⁺ doping have been prepared at room temperature through a soft chemical route, namely the chemical co-precipitation method. The nanostructures of the prepared nanoparticles have been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), selected-area electron diffraction (SAED), and UV-vis spectrophotometer. The sizes of as prepared nanoparticles are found to be in 1–4 nm range. Room-temperature photoluminescence (PL) spectrum of the undoped sample exhibits emission in the blue region with multiple peaks under UV excitation. On the other hand, in the Co²⁺ doped ZnS samples enhanced visible light emissions with emission intensities of ~35 times larger than that of the undoped sample are observed under the same UV excitation wavelength of 280 nm.     

Optical properties of ZnO nanoparticles synthesized by varying the sodium hydroxide to zinc acetate molar ratios using a Sol-Gel process

Material property dependence on the OH⁻/Zn²⁺ molar ratio of the precursor was investigated by varying the amount of NaOH during synthesis of ZnO. It was necessary to control the water content and temperature of the mixture to ensure the reproducibility. It was observed that the structural properties, particle size, photoluminescence intensity and wavelength of maximum intensity were influenced by the molar ratio of the precursor. The XRD spectra for ZnO nanoparticles show the entire peaks corresponding to the various planes of wurtzite ZnO, indicating a single phase. UV measurements show the absorption that comes from the ZnO nanoparticles in visible region. The absorption edge of these ZnO nanoparticles are shifted to higher energies and the determined band gap energies are blue shifted as the OH⁻/Zn² molar ration increases, due to the quantum confinement effects. The photoluminescence characterization of the ZnO nanostructures exhibited a broad emission band centred at green (600 nm) region for all molar ratios except for OH⁻/Zn²⁺ = 1.7 where a second blue emission around 468 nm was also observed. The photoluminescence properties of ZnO nanoparticles were largely determined by the size and surface properties of the nanoparticles.     

Photoluminescence and photoconductive characteristics of hydrothermally synthesized ZnO nanoparticles

In the present paper, ZnO nanoparticles (NPs) with particle size of 20–50 nm have been synthesized by hydrothermal method. UV-visible absorption spectra of ZnO nanoparticles show absorption edge at 372 nm, which is blue-shifted as compared to bulk ZnO. Photoluminescence (PL) and photoconductive device characteristics, including field response, light intensity response, rise and decay time response, and spectral response have been studied systematically. The photoluminescence spectra of these ZnO nanoparticles exhibited different emission peaks at 396 nm, 416 nm, 445 nm, 481 nm, and 524 nm. The photoconductivity spectra of ZnO nanoparticles are studied in the UV-visible spectral region (366–691 nm). In spectral response curve of ZnO NPs, the wavelength dependence of the photocurrent is very close to the absorption and photoluminescence spectra. The photo generated current, I_pc = (I_total - I_dark) and dark current I_dc varies according to the power law with the applied field I_pcαV^r and with the intensity of illumination I_pcαI_L ^r, due to the defect related mechanism including both recombination centers and traps. The ZnO NPs is found to have deep trap of 0.96 eV, very close to green band emission. The photo and dark conductivities of ZnO NPs have been measured using thick film of powder without any binder.     

Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

Synthesis, characterization and optical properties of water-soluble ZnS:Mn nanoparticles

ZnS nanoparticles with Mn²⁺ doping (0.5-20%) have been prepared through a simple chemical method, namely the chemical precipitation method. The structure of the nanoparticles has been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV-vis spectrometer. The size of the particles is found to be 3-5 nm range. Photoluminescence spectra were recorded for undoped ZnS nanoparticles using an excitation wavelength of 320 nm, exhibiting an emission peak centered at around 445 nm. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn²⁺⁴T₁-⁶A₁ transition is observed along with the blue emission. The prepared Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission 580 nm with the blue emission suppressed. The maximum PL intensity is observed only at the excitation energy of 3.88 eV (320 nm). Increase in stabilizing time up to 48 h in de-ionized water yields the enhancement of emission intensity of doped (4% Mn²⁺) ZnS. The correlation made through the concentration of Mn²⁺ versus PL intensity resulted in opposite trend (mirror image) of blue and yellow emissions.     

Synthesis and characterization of ZnO:Co<Superscript>2+</Superscript> nanoparticles

This work investigates cobalt doped ZnO nanoparticles prepared by using wet chemical methods. The nanoparticles have a typical size of 3–8 nm. The electronic structure as well as the optical and magnetic properties of Co²⁺ have been characterized. X-ray diffraction spectra of the powder show wurtzite ZnO with no secondary Co phases. In the energy range below the bandgap, the optical absorption spectra show the internal d–d transitions related to Co²⁺ incorporated on the Zn lattice site in ZnO. Low temperature photoluminescence measurements confirm these results. Based on the analysis of the g-valuesfor bulk ZnO:Co., electron paramagnetic resonance measurements coincide with the simulation of Co-doped ZnO powder. Thus far, no evidence for ferromagnetism has been obtained. PACS 61.46.Df; 76.30.Fc; 78.67.Bf     

Preparation of Cu<Superscript>2+</Superscript>/NTA-derivatized branch polyglycerol magnetic nanoparticles for protein adsorption

In this report, we described the preparation of Cu²⁺/nitrilotriacetic acids (NTA)-derivatized branch polyglycerol magnetic nanoparticles for protein adsorption with avoidance of nonspecific interactions at the same time. Magnetic nanoparticles (MNPs) were synthesized by the coprecipitation method. The transmission electron microscopy results showed that the average diameter of MNPs was 15.8 ± 4.6 nm. X-ray photoelectron spectroscopy and Fourier Transform infrared measurements indicated that branch polyglycerols were grafted on MNPs via the ring-opening polymerization of glycidol and that Cu²⁺ ions had been successfully immobilized on the surface of MNPs. The protein immobilization effect was characterized by UV–Vis spectrum. The results proved that Cu²⁺/NTA-derivatized branch polyglycerol magnetic nanoparticles effectively adsorbed bovine haemoglobin and rarely adsorbed lysozyme and γ-globin.     

Effect of doping and annealing on the physical properties of ZnO:Mg nanoparticles

Well-dispersed undoped and Mg-doped ZnO nanoparticles with different doping concentrations at various annealing temperatures are synthesized using basic chemical solution method without any capping agent. To understand the effect of Mg doping and heat treatment on the structure and optical response of the prepared nanoparticles, the samples are characterized using X-ray diffraction (XRD), energy-dispersive X-ray (EDX), UV–Vis optical absorption, photoluminescence (PL), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements. The UV–Vis absorbance and PL emission show a blue shift with increasing Mg doping concentration with respect to bulk value. UV–Vis spectroscopy is also used to calculate the band-gap energy of nanoparticles. X-ray diffraction results clearly show that the Mg-doped nanoparticles have hexagonal phase similar to ZnO nanoparticles. TEM image as well as XRD study confirm the estimated average size of the samples to be between 6 and 12 nm. Furthermore, it is seen that there was an increase in the grain size of the particles when the annealing temperature is increased.     

Ultrasonic induced photoluminescence decay in sonochemically obtained cauliflower-like ZnO nanostructures with surface 1D nanoarrays

Cauliflower-like ZnO nanostructures with average crystallite size of about 55 nm which have surface one dimensional (1D) nanoarrays with 10 nm diameter were successfully fabricated through a simple sonochemical route. X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and room temperature photoluminescence (PL) characterizations were performed to investigate the morphological and structural properties of the obtained nanostructures. It has been shown that the synthesized cauliflower-like ZnO nanostructures irradiated UV luminescence and a green peak in visible band. Ultrasonic post-treatment of the particles for about 2 h increased the density of surface defects resulted in an increase in the green emission intensity.     

Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb sol gel derived phosphor

Terbium (1 mol%) doped ZnO-SiO₂ binary system was prepared by a sol-gel process. Nanoscopic effects of ZnO on the photoluminescence (PL) and the cathodoluminescence (CL) properties were studied. Defects emission from ZnO nanoparticles was measured at 560 nm and the line emission from Tb³⁺ ions in SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺ with a major peak at 542 nm was measured. The PL excitation wavelength for 542 nm Tb³⁺ emission was measured at ∼320 nm in both SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺. The CL data showed quenched luminescence of the ZnO nanoparticles at 560 nm from a composite of ZnO-SiO₂:Tb³⁺ and a subsequent increase in 542 nm emission from the Tb³⁺ ions. This suggests that energy was transferred from the ZnO nanoparticles to enhance the green emission of the Tb³⁺ ions. The PL and CL properties of ZnO-SiO₂:Tb³⁺ binary system and possible mechanism for energy transfer from the ZnO nanoparticles to Tb³⁺ ions are discussed.     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

Intense Upconversion Luminescence of Yb<Superscript>3+</Superscript>-Er<Superscript>3+</Superscript> in Li<Subscript>2</Subscript>O Content Tungsten-tellurite Glasses

The Er³⁺ -Yb³⁺ codoped in Li₂O content tungsten -tellurite (TWL) transparent glasses are synthesized and measured the absorption, Raman and upconversion luminescence (UPL) spectra. At room temperature intense green emission peak at 560 nm ( ⁴S_3/2→⁴I_15/2) and red emission peak at 670 nm ( ⁴F_9/2→⁴I_15/2) of Er³⁺ observed even at minimum 86 mW pumping power of infrared 980 nm excitation. For structure of the TWL glass, Raman spectrum result revealed that an important role of WO₃ in the formation of glass network linkage with Li₂O. Under this influence estimated lifetime of the ⁴I_11/2 of Er³⁺ was 1.89 μs and due to lower phonon energy of the glass produce strong upconversion signal. The effect of Er₂O₃ concentration on emission intensity result indicated that green emission intensity initially increase in compare to red emission. Under the 980 nm pump power variation measured the relatively increases the red emission to the green emission intensity and analyze the possible upconversion mechanism and process.