Structure and ferromagnetic properties of Co-doped ZnO powders

Single-phase Zn_1−xCo_xO (x=0.02, 0.04) powders were synthesized by a simple co-precipitation technique. X-ray diffraction analysis reveals that the Co-doped ZnO crystallizes in a wurtzite structure. The lattice constants of Co-doped ZnO powders decrease slightly when Co is doped into ZnO. Optical absorption spectra show a decrease in the bandgap with increasing Co content and also give an evidence of the presence of Co²⁺ ions in tetrahedral sites. Raman spectra indicate that Co doping increased the lattice defects and induced another Raman vibration mode around at 538 cm⁻¹, which is an indicator for the incorporation of Co²⁺ ions into the ZnO host matrix. Magnetic measurement reveals that the Zn_1−xCo_xO (x=0.02, 0.04) powders clearly exhibit room-temperature ferromagnetic behavior, which makes them potentially useful as building components for spintronics.     

Swift heavy ion induced modifications in cobalt doped ZnO thin films: Structural and optical studies

Modifications in the structural and optical properties of 100 MeV Ni⁷⁺ ions irradiated cobalt doped ZnO thin films (Zn_1−xCo_xO, x = 0.05) prepared by sol-gel route were studied. The films irradiated with a fluence of 1 × 10¹³ ions/cm² were single phase and show improved crystalline structure with preferred C-axis orientation as revealed from XRD analysis. Effects of irradiation on bond structure of thin films were studied by FTIR spectroscopy. The spectrum shows no change in bonding structure of Zn-O after irradiation. Improved quality of films is further supported by FTIR studies. Optical properties of the pristine and irradiated samples have been determined by using UV-vis spectroscopic technique. Optical absorption spectra show an appreciable red shift in the band gap of irradiated Zn_1−xCo_xO thin film due to sp-d interaction between Co²⁺ ions and ZnO band electrons. Transmission spectra show absorption band edges at 1.8 eV, 2.05 eV and 2.18 eV corresponding to d-d transition of Co²⁺ ions in tetrahedral field of ZnO. The AFM study shows a slight increase in grain size and surface roughness of the thin films after irradiation.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Formation of room-temperature ferromagnetic Zn1−xCoxO nanocrystals

Optical and magnetic properties of Co²⁺-doped ZnO nanocrystals were studied. Optical measurements confirm the incorporation of Co²⁺ in ZnO lattice with tetrahedral geometry. Optical absorption spectra also reveal the partial bleaching of the excitonic feature attributable to an increase in electron concentration. Magnetization measurements indicate the ferromagnetic ordering in Co²⁺-doped ZnO nanocrystals with saturation magnetization . No structural changes were observed in lightly doped ZnO nanocrystals. The present investigations are important in obtaining the ferromagnetic Zn_1−xCo_xO nanocrystals.     

X-ray absorption spectroscopic and magnetic characterization of cobalt-doped zinc oxide nanocrystals prepared by the molten-salt method

The local atomic arrangement and electronic structure of the Co-doped Zn_1−xCo_xO nanocrystal have been quantitatively examined along with its magnetic properties. According to our analysis using powder X-ray diffraction, electron microscopy, and Zn K-edge X-ray absorption spectroscopy (XAS), phase-pure wurzite-structured Zn_1−xCo_xO nanocrystals have been successfully synthesized via the molten-salt method. The Co K-edge XAS analysis clearly demonstrates that all the Co²⁺ ions are substituted for the tetrahedral Zn sites of the Wurzite structure with a coordination number of 3.9 and a bond distance of 1.97 Å, ruling out the presence of magnetic impurity phase and Co-metal cluster. Magnetization measurements reveal that the present Zn_1−xCo_xO sample does not show any ferromagnetic transition down to 2 K. In this regard, we can conclude that Co-doped zinc oxide is not ferromagnetic but the previously reported ferromagnetism in this phase would be an extrinsic property.     

Optical properties of bulk Zn1−xCoxO magnetic semiconductors

Polycrystalline Zn_1−xCo_xO (x=0, 0.02, 0.05, 0.10 and 0.15) oxides have been synthesized by solid state reaction via sintering ZnO and Co powders in open air. X-ray diffraction analyses using Rietveld refinement indicate that a stoichiometric single phase with a wurtzite-like structure was found in Zn_1−xCo_xO samples with x up to 0.10. The elemental mapping using energy dispersive X-ray spectroscopic analyses presents a uniform distribution of Co. Optical transmittance measurements show that several extra absorption bands appear in the Co-doped ZnO, which is due to the transitions between the crystal-field-split 3d levels of tetrahedral Co²⁺ substituting Zn²⁺ ions. Raman measurements show that limited host lattice defects are induced by Co doping. Magnetization measurements reveal that the Co-doped ZnO samples are paramagnetic due to the absence of free carriers and in low temperature the dominant magnetic interaction is nearest-neighbor antiferromagnetic.     

Syntheses of optically efficient (La1−x−yCexTby)F3 nanocrystals via a hydrothermal method

Optically efficient cerium and terbium doped lanthanide fluoride (La_1−x−yCe_xTb_y)F₃ nanocrystals with different doping concentrations have been synthesized by a hydrothermal route in the presence of ethylenediamine tetraacetic acid disodium salt (EDTA). The results showed that the formation of nanocrystals with different morphologies depends on terbium ion Tb³⁺ doping concentration, but independent of cerium ion Ce³⁺ doping concentration. With increase in Tb³⁺ doping concentration, the morphologies of nanocrystals evolved from a spherical shape to a plated-like one. In addition, both the photoluminescence quantum yield (PL QY) and the fluorescence lifetime of nanocrystals increased with the increase in Ce³⁺ doping concentration in cerium and terbium co-doped system. The PL QY reached up to 55%, and the lifetime up to 7.3 ms. Transmission electron microscopy (TEM), X-ray diffraction (XRD), selected area electron diffraction (SAED), X-ray fluorescence (XRF), energy dispersive spectroscopy (EDS), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) and infrared (IR) spectroscopies were employed to characterize the properties of nanocrystals. The growth mechanism of nanocrystals with different morphologies and optical properties of nanocrystals with different doping concentrations were investigated.     

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

Magnetic and Raman scattering studies of Co-doped ZnO thin films grown by pulsed laser deposition

Phase pure Zn_1?x Co _x O thin films grown by pulsed laser deposition have transmittance greater than 75 % in the visible region. Raman studies confirm the crystalline nature of Zn_1?x Co _x O thin films. Zn_0.95Co_0.05O thin films show room temperature ferromagnetism with saturation magnetization of 0.4μ _B /Co atom. The possible origin of paramagnetism at higher Co doping concentrations can be attributed to the increased nearest-neighbor antiferromagnetic interactions between Co²⁺ ions in ZnO matrix. XPS confirms the substitution of Co²⁺ ions into the ZnO host lattice.     

Optical and ESR studies on Fe doped ZnS nanocrystals

Zn_1 − xFe_xS (x=0.0, 0.1, 0.2, 0.4 and 0.6) nanocrystals have been obtained by chemical co-precipitation from homogeneous solutions of zinc and iron salt compounds, with S²⁻ as precipitating anion formed by decomposition of thiophenol. The TEM micrographs show a spherical shape for ZnS nanocrystals and their average size is around 7 nm. The optical absorption spectra indicate a blue shift of the absorption edge with increasing Fe-content. The luminescence of nanoparticles excite at about 370 nm with an emission peak at around 490 nm. At room temperature, ESR signal characteristic of Fe³⁺ was observed in samples of all concentrations.     

Microstructures, surface bonding states and room temperature ferromagnetisms of Zn0.95Co0.05O thin films doped with copper

Zn_0.95−xCo_0.05Cu_xO (ZCCO, where x = 0, 0.005, 0.01 and 0.015) thin films were deposited on Si (1 0 0) substrates by pulsed laser deposition technique. Crystal structures, surface morphologies, chemical compositions, bonding states and chemical valences of the corresponding elements for ZCCO films were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and X-ray photoelectron spectroscopy (XPS). XRD and FESEM results indicate that crystallite sizes of the highly (0 0 2)-oriented ZCCO films slightly decrease with increasing Cu content. When the Cu content increases from 0 to 0.015, Zn 2p_3/2, Co 2p, Cu 2p_3/2 and O 1s peaks of the ZCCO film shift towards higher or lower binding energy regions, and the reasons for these chemical shifts are investigated by fitting the corresponding XPS narrow-scan spectra. Both in-plane and out-of-plane magnetization-magnetic field hysteresis loops of the ZCCO films reveal that all the films have room temperature ferromagnetisms (RTFMs). The conceivable origin of the RTFM is ascribed to the combined effects of the local structural disorder resulted from (Co²⁺, Cu²⁺, Cu¹⁺)-cations which substitute Zn²⁺ ions in the ZnO matrices, ferromagnetic coupling between coupled dopant atoms caused by Co²⁺ (3d⁷4s⁰) and Cu²⁺ (3d⁹4s⁰) spin states, and exchange interactions between the unpaired electron spins originating from lattice defects induced by Cu doping in the Zn_0.95Co_0.05O matrices.     

Properties of Co/Ni codoped ZnO based nanocrystalline DMS

Nanoparticles of Co and Ni codoped zinc oxide, Zn_0.9Co_0.1−xNi_xO (x=0.0, 0.03, 0.06 and 0.09), diluted magnetic semiconductors (DMSs) are synthesized by the sol-gel method at annealing temperature of 500 °C. X-ray diffraction (XRD) patterns confirm the single phase character of the samples with x=0.0 and 0.03. However, minor NiO secondary phase is detected in the samples with x=0.06 and 0.09. All of them possess the hexagonal wurtzite structure. There is no significant change in the lattice parameters due to variation of doping concentration. The average particle size is found to be 19.31-25.71 nm. FTIR and UV-vis spectroscopic results confirm the incorporation of the dopants into the ZnO lattice structure. Magnetization data reveal the presence of room temperature ferromagnetism (RTFM). The XRD patterns rule out the formation of secondary phase of either metallic Co cluster or CoO in the samples. Nevertheless, the secondary phases are a concern in any DMS system as a source of spurious magnetic signals. Therefore, we carried out the XPS studies from which the oxidation states of Co and Ni are found to be Co²⁺ and Ni²⁺, respectively. Moreover, XPS O 1s spectra show evidence of the presence of the oxygen vacancy in the ZnO matrix.     

A simple synthesis and magnetic behavior of nanocrystalline Zn0.9Co0.1O powders by using Zn and Co acetates and polyvinyl pyrrolidone as precursors

This paper reports the synthesis of nanocrystalline powders of Co-doped ZnO (i.e. Zn_0.9Co_0.1O (ZCO)) diluted magnetic semiconductor by a simple method using acetate salts of Zn and Co, and polyvinyl pyrrolidone as precursors. The morphology and crystalline size of the synthesized powders were evaluated by scanning electron microscopy and transmission electron microscopy (TEM). The ZCO powders consist of both nanoparticles with particle sizes of ∼50–100 nm and nanorods with diameters of ∼100–200 and ∼200–500 nm in length. The X-ray diffraction and TEM results indicated that the synthesized ZCO powders had the pure wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co ions in substitution of Zn ions. Room-temperature magnetization results revealed a paramagnetic behavior for the ZCO precursor (as grown sample) and a ferromagnetic behavior for the ZCO powders calcined in air at 873 K for 1 h.     

Room temperature ferromagnetism in Zn1−xCoxS thin films with wurtzite structure

The magnetic properties of Zn_1−xCo_xS (x=0.025 and 0.05) thin films grown on α-quartz substrates at different temperatures (T_S) of 200, 400 and 600 °C by means of pulsed laser deposition are presented. The films are crystallized with wurtzite structure. Optical absorption and transmission electron microscopy measurements indicate that Co ions are substituted to Zn on tetrahedral sites. Their magnetic response is composed of ferromagnetic and paramagnetic components of which respective strengths depend on T_S and Co concentration. This behavior is interpreted as due to fluctuations in the magnetic ordering, depending on grain size and site location in grain boundaries or in crystal cores.     

Magnetic properties of cobalt substituted M-type barium hexaferrite prepared by co-precipitation

The co-precipitation and solid state methods were used in the synthesis of barium hexaferrite (BaM). Phase pure BaM was obtained with 1, 2, 3, 5, 10, 15, 20 and 30 wt% cobalt oxide (Co₃O₄). The addition of Co^2+/3+ ions to the BaM increased the permeability and magnetic loss tangent to a value of 3.5 at 5% and reduced to 1 at 30% doping. With increased Co doping, M_s was reduced from 87-58 emu/g, M_r increased from 11 to 40 emu/g with 3–5 wt% Co and 9 emu/g for 30% doping. H_c sharply increased from 540 to 2200 Oe with a reduction to 280 Oe at 10 K with increasing temperature to 300 K. T_c increased from 740 to 750 K for 30% Co doping. DTA–TGA studies of green body showed decarboxilation to occur at around 825 °C and the transformation of residual Co₃O₄ to Co₂O₃ at around 577 °C. The XRD data confirmed the Co ions substituting into Fe sites until a 10–15% doping level where the structure altered to W-type hexaferrite. The densities of the compounds varied with doping to a maximum of 4.45 g/cm³.     

High-temperature ferromagnetism in cobalt-doped ZnO single-crystalline nanorods

Co-doped ZnO single-crystalline nanorods with 80–100 nm in diameter and 1.5–2 μm in length have been prepared in a simple solution route. X-ray diffraction data and selected area electron diffraction pattern of the diluted magnetic semiconductor nanorods confirm the single crystallinity of Zn_1−xCo_xO solid solution without impurities of metallic Co or other phases. Magnetic results show that the Zn_0.95Co_0.05O nanorods exhibit a ferromagnetic characteristic with Curie temperature higher than 380 K. The high-temperature ferromagnetic properties allow this Zn_1−xCo_xO nanorods potential applications in future spintronic devices.     

Structural and optical properties of ZnO nanorods grown on MgxZn1−xO buffer layers

ZnO nanorod arrays were synthesized by chemical-liquid deposition techniques on Mg_xZn_1−xO (x = 0, 0.07 and 0.15) buffer layers. It is found that varying the Mg concentration could control the diameter, vertical alignment, crystallization, and density of the ZnO nanorods. The X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) data show the ZnO nanorods prefer to grow in the (0 0 2) c-axis direction better with a larger Mg concentration. The photoluminescence (PL) spectra of ZnO nanorods exhibit that the ultraviolet (UV) emission becomes stronger and the defect emission becomes weaker by increasing the Mg concentration in Mg_xZn_1−xO buffer layers.     

Investigations on structural and optical properties of Zn1−xGdxS nanoparticles

Zn_1−xGd_xS (x = 0.00, 0.02 and 0.04) nanoparticles were synthesized by facile chemical co-precipitation method using PVP as a surfactant. ZnS nanoparticles could be doped with Gd ions during synthesis without altering the XRD patterns of ZnS. Also, the pattern of the powders showed cubic zincblende structure. The particle size obtained from the XRD studies lies in the range 3-5 nm, whereas from TEM analysis it is 4 nm for x = 0.02 sample. The UV-Vis absorption spectra revealed that Zn_1−xGd_xS nanoparticles exhibit strong confinement effect as the blue shift in the absorption spectra with that of the undoped ZnS. The photoluminescence spectra showed enhanced luminescence intensity and the entry of Gd into host lattice.