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.     

Low-temperature growth of ZnO nanorods on PET fabrics with two-step hydrothermal method

An effective low-temperature growth method to fabricate hexagonally oriented ZnO nanorod arrays onto PET fabrics is reported. The effect of substrate pre-treatment and C₆H₁₂N₄ concentration on the structure of ZnO nanorod arrays were investigated in details by X-ray diffraction (XRD), FE-SEM and ultraviolet protection factor (UPF). The results show that substrate pre-treatment, C₆H₁₂N₄ concentration indeed have great influence on the growth of ZnO nanorod arrays. It is indispensable to introduce a ZnO seed layer on the substrate and under growth condition of n(C₆H₁₂N₄):n[Zn(NO₃)₂] = 1:1, T = 90 °C, t = 3 h, the well-aligned ZnO nanorod arrays with 40-50 nm in diameter and 300-400 nm in length were achieved on the pre-treated PET fabrics. The ZnO nanorods grown on PET fabrics possessed an ultrahigh ultraviolet protection factor of 480.52 in this study, indicating an excellent protection against ultraviolet radiation in comparison with the untreated PET fabrics.     

Thermally stable blue-emitting NaSrPO4:Eu phosphor for near UV white LEDs

A novel blue light emitting NaSr_1 − xPO₄:Eu²⁺_x (x = 0.001 to 0.02) phosphors were prepared by solid-state reaction method to investigate its optical properties and thermal stability for its application in white light-emitting diodes (w-LEDs). The excitation and emission spectra of the prepared phosphor reveal a broad emission peak centered at 460 nm which arises due to 4f-5d transitions of Eu²⁺ upon the near ultra-violet (n-UV) excitation wavelength at 380 nm. The effect of Eu²⁺ doping concentration and sintering temperature on the emission intensity of NaSrPO₄:Eu²⁺ was investigated along with its chromaticity coordinates. The temperature dependent luminescence properties of the prepared phosphor show better results than that of the commercial YAG:Ce³⁺phosphor. Besides, their XRD, FT-IR, SEM, TG, and DTA profiles have also been analyzed to explore its structural details.     

Synthesis and characterization of Ni-doped ZnO: A transparent magnetic semiconductor

We report synthesis of a transparent magnetic semiconductor by incorporating Ni in zinc oxide (ZnO) matrix. ZnO and nickel-doped zinc oxide (ZnO:Ni) thin films (∼60 nm) are prepared by fast atom beam (FAB) sputtering. Both undoped and doped films show the presence of ZnO phase only. The Ni concentration (in at%) as determined by energy dispersive X-ray (EDX) technique is ∼12±2%. Magnetisation measurement using a SQUID magnetometer shows that the Ni-doped films are ferromagnetic, having coercivity (H_c) values 192, 310 and 100 Oe and saturation magnetization (M_s) values of 6.22, 5.32 and 4.73 emu/g at 5, 15 and 300 K, respectively. The Ni-doped film is transparent (>80%) across visible wavelength range. Resistivity of the ZnO:Ni film is ∼2.5×10⁻³ Ω cm, which is almost two orders of magnitude lower than the resistivity (∼4.5×10⁻¹ Ω cm) of its undoped counterpart. Impurity d-band splitting is considered to be the cause of increase in conductivity. Interaction between free charges generated by doping and localized d spins of Ni is discussed as the reason for ferromagnetism in the ZnO:Ni film.     

Ultrafast laser assisted fabrication of ZnO nanorod arrays for photon detection applications

Orderly aligned ZnO nanorod arrays were grown by the ultrafast laser assisted ablation deposition method. These nanorod arrays were further used to make efficient p-n heterojunction photodetector arrays, which have the potential to have nanoscale spatial resolution for imaging, unique incident polarization discrimination capability, and much improved quantum efficiency as well as detection sensitivity. Both front- and back-illumination photodetection schemes were demonstrated by growing those ZnO nanorod arrays on p-type silicon and p-type Zn_0.9Mg_0.1O-coated Al₂O₃ (0 0 0 1) substrates, respectively. Typical diode rectification behavior and photosensitivity were observed in both designs through I-V and photocurrent measurements.     

Photoluminescence characteristics of ZnO doped with Eu powders

In this work, we have investigated the photoluminescence spectra of europium-doped zinc oxide crystallites prepared by a vibrating milled solid-state reaction method. X-ray diffraction, scanning electron microscopy, luminescence spectra and time-resolved spectra analysis were used to characterize the synthetic ZnO:Eu³⁺ powders. XRD results of the powders showed a typical wurtzite hexagonal crystal structure. A second phase occurred at 5 mol% Eu₂O₃-doped ZnO. The ⁵D₀-⁷F₁ (590 nm) and ⁵D₀-⁷F₂ (609 nm) emission characteristics of Eu³⁺ appeared after quenching with more than 1.5 mol% Eu₂O₃ doping. The Commission Internationale d’Eclairage (CIE) chromaticity coordinates of a ZnO:Eu³⁺ host excited at λ_ex=467 nm revealed a red-shift phenomenon with increase in Eu³⁺ ion doping. The lifetime of the Eu³⁺ ion decreased as the doping concentration was increased from 1.5 to 10 mol%, and the time-resolved ⁵D₀→⁷F₂ transition presents a single-exponential decay behavior.     

Photoluminescence and Raman scattering of Cu-doped ZnO films prepared by magnetron sputtering

The Cu-doped ZnO films were prepared by direct current reactive magnetron sputtering using a zinc target with various Cu-chips attached. The influences of Cu-doping on the microstructure, photoluminescence, and Raman scattering of ZnO films were systematically investigated. The results indicate that ZnO films doped with moderate Cu dopant (2.0-4.4 at.%) can obtain wurtzite structure with strong c-axis orientation. The near band edge (NBE) emission of ZnO film can be enhanced by Cu dopant with a concentration of 2.0 at.% and quench quickly with further increase of doping concentration. Two additional modes at about 230 and 575 cm⁻¹, which could be induced by Cu dopant, can be observed in Raman spectra of the Cu-doped ZnO films.     

Improvement of ZnO nanorod-based dye-sensitized solar cell efficiency by Al-doping

The current study investigates the performance of dye-sensitized solar cells (DSSCs) based on Al-doped and undoped ZnO nanorod arrays synthesized by a simple hydrothermal method. Current density-voltage (J-V) characterizations indicate that Al-doping in ZnO crystal structure can significantly improve current densities and the energy conversion efficiency (η) of ZnO nanorod-based DSSCs. The maximum η, 1.34%, was achieved in DSSC when Al-doped ZnO nanorod arrays were grown in 0.04 M zinc acetate dihydrate solution with 5 mM aluminum nitrate nonahydrate. This result represents a large increase of η in Al-doped ZnO nanorod-based DSSCs as compared to undoped (0.05%). The improved DSSC photovoltaic performance can be attributed to two main factors: (1) increased light harvesting efficiency due to a large amount of N719 adsorbed on the large surface area of Al-doped ZnO nanorod arrays, and (2) increased electrical conductivity due to A1³⁺ ion doped into the ZnO lattice at the divalent Zn²⁺ site, allowing electrons to move easily into the Al-doped ZnO conduction band.     

A new blue-emitting phosphor, SrZnO2:Pb, synthesized by the adipic acid templated sol-gel route

A new blue-emitting phosphor, Sr_1−xPb_xZnO₂, was prepared by a novel adipic acid templated sol-gel route. Photoluminescence and crystalline properties were investigated as functions of calcination temperatures and the Pb²⁺ doping levels. It was found that under UV excitation with a wavelength of 283 or 317 nm, the phosphors gave emission from 374 to 615 nm with a peak centered at 451 nm. This broad-band was composed of UV and the visible range was attributed to an impurity-trapped exciton-type emission. The maximum emission intensity of the Sr_1−xPb_xZnO₂ phosphors occurred at a Pb concentration of x=0.01. The decay time was observed to be ∼33 ms for the compound doped with 1 mol% Pb prepared at 1000 °C. Diffuse reflectance spectra revealed the characteristic absorption peaks and the bandgap energy of SrZnO₂ was found to be 3.4 eV. SEM analysis indicated that phosphor particles have an irregularly rounded morphology and the average particle size was found to be approximately 1 μm.     

Controllable vertical growth onto anatase TiO2 nanoparticle films of ZnO nanorod arrays and their photoluminescence and superhydrophilic characteristics

Well-aligned ZnO nanorod arrays have been successfully fabricated directly on anatase TiO₂ nanoparticle films via low-temperature hydrothermal processes. The effects of the reactive time, temperature and reactant concentration on the growth of the as-prepared ZnO crystals are investigated in detail, and the possible mechanisms of crystal ZnO nanorod growth are also suggested. The results show that the low reactant concentration is in favor of the increase in the aspect ratio of crystal ZnO nanorods with weak orientation, while the long reactive time and high reactant concentration are useful to prepare well-aligned crystal ZnO nanorod arrays. Interestingly, the typically constructed composite films exhibit superhydrophilic characteristic without UV irradiation. Moreover, a strong near-ultraviolet PL band centering at about 385 nm and a weak green PL band centering at about 525 nm can appear at the room temperature.     

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.     

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.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

Influence of Hf doping concentration on microstructure and optical properties of HfxZn1−xO thin films

Hf_xZn_1−xO thin films (x=3, 7, 10 and 15 mol%) were deposited on Si (1 0 0) using pulsed laser deposition. The influence of the Hf concentration on the microstructure and optical properties of the films was studied. It is found that Hf ions can be effectively doped into ZnO and all films crystallize in the hexagonal wurtzite structure with a preferred c-axis orientation. The lattice constants of Hf_xZn_1−xO films increase with the Hf contents. Two ultraviolet peaks centered at about 364 and 380 nm coexist in the fluorescent spectra. With increasing the Hf contents, the intensity of fluorescent peaks enhances remarkably. At the same time the energy gaps gradually increase, while the positions of ultraviolet peaks remain unchanged. The mechanism of luminescent emission for Hf_xZn_1−xO films was discussed.     

Enhancement of optical properties and donor-related emissions in Y-doped ZnO

The Zn_1−xY_xO nanoparticles with good optical properties have been prepared by sol–gel method. The yttrium doping effect on the structures and optical properties were investigated by XRD, SEM, XPS and low temperature photoluminescence. The UV emission intensity of yttrium doped ZnO was over 300 times stronger than that of pure ZnO, which was an exciting result in enhancing the ultraviolet near band edge emission in photoluminescence from ZnO nanoparticles. The UV emission band of doped ZnO nanoparticles exhibits a red shift from 388 to 398 nm, indicating a shallow energy level near valence band has been formed due to the yttrium doping into ZnO lattices. The defect-related band is suppressed (I_D/I_UV = 1–0.83) considerably in Zn_1−xY_xO nanoparticles, revealing the quenching of the broad yellow-orange emission. The doping effect on the optical properties is investigated by temperature dependent photoluminescence. The experimental results indicated that the donor level of yttrium is deeper than that of undoped ZnO.     

Structural, magnetic and transport properties of Ni-doped ZnO films

In this work, Ni-doped ZnO (Zn_1−xNi_xO, x=0, 0.03, 0.06, 0.11) films were prepared using magnetron sputtering. X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), temperature dependence electrical resistance, Hall and magnetic measurements were utilized in order to study the properties of the Ni-doped ZnO films. XRD and XAS results indicate that all the samples have a ZnO wurtzite structure and Ni atoms incorporated into ZnO host matrix without forming any secondary phase. The Hall and electrical resistance measurements revealed that the resistivity increased by Ni doping, and all the Ni-doped ZnO films exhibited n-type semiconducting behavior. The magnetic measurements showed that for the samples with x=0.06 and 0.11 are room-temperature ferromagnetic having a saturation magnetization of 0.33 and 0.39 μ_B/Ni, respectively. The bound-magnetic-polaron mediated exchange is proposed to be the possible mechanism for the room-temperature ferromagnetism in this work.     

Structural, magnetic properties and photoemission study of Ni-doped ZnO

Nickel-doped ZnO (Zn_1−xNi_xO) have been produced using rf magnetron sputtering. X-ray diffraction measurements revealed that nickel atoms were successfully incorporated into ZnO host matrix without forming any detectable secondary phase. Ni 2p core-level photoemission spectroscopy confirmed this result and suggested Ni has a chemical valence of 2+. According to the magnetization measurements, no ferromagnetic but paramagnetic behavior was found for Zn_0.86Ni_0.14O. We studied the electronic structure of Zn_0.86Ni_0.14O by valence-band photoemission spectroscopy. The spectra demonstrate a structure at ∼2 eV below the Fermi energy E_F, which is of Ni 3d origin. No emission was found at E_F, suggesting the insulating nature of the film.     

Effect of Bi on fluorescence properties of YPO4:Dy phosphors synthesized by a modified chemical co-precipitation method

Y_0.99−xPO₄:0.01Dy³⁺, xBi³⁺ (x=0, 0.01, 0.05, 0.10, 0.15, 0.20 and 0.25) phosphors have been synthesized by a modified chemical co-precipitation method using urea as a pH value regulator. The samples were characterized by X-ray powder diffraction (XRD) and photoluminescence spectroscopy. XRD results show that the samples have only single tetragonal structure when x≤0.15, but extraneous BiPO₄ phase appears besides major tetragonal phase when x≥0.20. The crystallinity of the samples is found to improve with increasing Bi³⁺ ion concentration from 0 to 15 mol%, and then decreased for higher concentrations associated with increasing BiPO₄ phase. Photoluminescence excitation spectra results show that the phosphor can be efficiently excited by ultraviolet light from 250 to 400 nm including four peaks at 294, 326, 352 and 365 nm. Emission spectra exhibit strong blue emission (483 nm) and another strong yellow emission (574 nm). When the Bi³⁺ ion concentration is 1 mol%, the intensity of excitation and emission spectra increased evidently. In addition, the yellow-to-blue emission intensity ratio (I_Y/I_B) is strongly related to the excitation wavelength and not to the Bi³⁺ ion concentration.     

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.     

Room temperature ferromagnetism in nanocrystalline Ni-doped ZnO synthesized by co-precipitation

Ni-doped ZnO powder was synthesized by thermal co-decomposition of a mixture of bis(acetylacetonato) zinc(II)hydrate and bis(dimethylglyoximato)nickel(II) complexes. The samples were characterised by X-ray diffraction (XRD), Energy dispersion X-ray fluorescence (EDXRF), and FT-IR spectroscopy. The atomic ratio Ni/Zn of the samples was determined by the EDXRF method to be 1%, 4.3%, 7.4% and 22.5 wt%. The XRD studies show the formation of nanocrystalline (14-18 nm) of Ni-doped ZnO along with nanoparticles of NiO. By magnetic measurements, it was observed that powder contains 1%Ni, 4.3%Ni, 7.4%Ni exhibits superparamagnetic behaviour while the sample of 22.5%Ni prepared in closed atmospheric environment shows clear ferromagnetic (FM) loop at room temperature due to the formation of solid solution Zn_1−xNi_xO.