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.     

Effect of annealing temperature on optical and magnetic properties of Cr doped ZnS nanoparticles

ZnS:Cr (3 at.%) nanoparticles were synthesized by chemical co-precipitation method using EDTA as capping agent. The samples were annealed in air for 3 h in steps of 100 °C in the temperature range of 200–700 °C. The effect of annealing temperatures on the structural and photoluminescence properties of Cr doped ZnS nanoparticles was investigated using X-ray Diffraction (XRD), a Scanning Electron Microscope (SEM), Energy Dispersive X-ray spectroscopy (EDS), Diffuse Reflectance Spectra (DRS), Vibrating Sample Magnetometer (VSM) and Photoluminescence (PL) techniques. EDS spectra confirmed the presence of Cr in the samples with expected stoichiometry. XRD studies confirmed the formation of ZnO above 500 °C. Photoluminescence studies on ZnS:Cr nanoparticles indicated that the emission wavelength is tunable in the range of 440–675 nm as a function of annealing temperature. VSM results indicated a decrease in ferromagnetism with increase in annealing temperature, perhaps due to appreciable variation in structural defects that are sensitive to annealing temperature.     

Effect of KOH molarity and annealing temperature on ZnO nanostructure properties

In this work, ZnO nanorods (NRs) were fabricated using a low cost chemical bath deposition (CBD) method. The effect of the potassium hydroxide concentration on the fabricated ZnO nanostructures was studied in depth. The optical, structure, and surface morphology properties of the fabricated ZnO nanostructures were investigated using Uv-vis spectroscopy, XRD, and SEM. The results indicate that the formation of hexagonally structured ZnO nanorods with different lengths and diameters was dependent on the KOH concentration. The sample prepared with 2 M of KOH was the best one for optoelectronic applications, since it has the smallest diameters. This sample was annealed at different temperatures (473 K–1073 K). Positron Annihilation Lifetime Spectroscopy was used to determine the defects in the ZnO nanorods. The results show that the positron mean lifetime (τ_m) decreased as the annealing temperature increased, which means that the overall defects in the ZnO nanorods decreased with increasing temperature. Consequently, higher performance semiconductor devices based on ZnO nanorods could be fabricated after high annealing of the ZnO nanorods.     

Enhancement of the ultraviolet emission of ZnO nanorods by terphenyl liquid-crystalline ligands modification

We have developed a novel method to modifying the surface of ZnO nanorods (ZnO NRs) using p-hexoxyterphenylol (HTph-OH) as liquid crystal ligands. The structure and morphology of the modified ZnO NRs were characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and atomic force microscopy (AFM). AFM measurement showed that the dispersion of ZnO NRs could be dramatically improved by the surface modification of HTph-OH and further annealing treatment at its liquid crystal state temperature (150 °C). The remarkable decrease of the annealed composite film roughness is because the HTph-OH chains self-organize into more ordered structure induced by mesogens after annealing treatment, which may push the ZnO NRs to form oriented nano-dispersing structure. The optical properties of the modified ZnO NRs were investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy (PL). Markedly enhanced band-edge ultraviolet photoluminescence and significantly reduced defect-related emission were observed. We attribute this observation to the nearly perfect surface passivation of the ZnO NRs by the HTph-OH molecules. Meanwhile, UV emission of modified ZnO NRs could be further enhanced by increasing the concentration of HTph-OH and annealing treatment at its liquid crystal state temperature.     

Effect of the reaction conditions on the formation of the ZnO nanostructures

ZnO nanorods were synthesized through a simple chemical method by reacting Zn(C₂H₃O₂)₂·2H₂O and NaOH at low temperature and the effects of changing the order of addition of reactants on the morphological evolution of ZnO nanorods were investigated. The samples were characterized by using XRD, SEM, EDX, TEM, BET and Raman techniques. Optical properties of the ZnO nanostructures were too investigated by UV–Vis spectroscopy at room temperature.The hexagonal wurtzite phase of ZnO was confirmed by X-ray diffraction (XRD) for all the samples. SEM and TEM analysis indicated that different morphologies were obtained by changing the order of addition of reactants.     

Synthesis,structural, optical and magnetic properties of Cu-doped ZnO nanorods prepared by a simple direct thermal decomposition route

Cu-doped ZnO nanorods (i.e. Cu = 1.75, 3.55, 5.17 and 6.39 at.%) have been successfully synthesized by simple, direct, thermal decomposition of zinc and copper acetates in air at 300 °C for 6 h. The prepared samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy. The XRD results indicate that the 1.75 at.% Cu-doped ZnO sample has a pure phase with the ZnO wurtzite structure, while the impurity phases are detected with increasing Cu concentrations. It was found that the doping of Cu results in a reduction of the preparation temperature. The optical properties of the samples were also investigated by UV–visible spectroscopy and photoluminescence measurements. The results show that the Cu doping causes the change in energy-band structures and effectively adjusts the intensity of the luminescence properties of ZnO nanorods. X-ray photoelectron spectroscopy analysis implies that there are some oxygen vacancies in the samples and also indicates that all the doped samples are associated with the mixture of Cu ion states (Cu²⁺ and Cu¹⁺/Cu⁰). Magnetic measurements by vibrating sample magnetometry indicate that undoped ZnO is diamagnetic, whereas all of the Cu-doped ZnO samples exhibit room temperature ferromagnetic behavior. We suggest that Cu substitution and density of oxygen vacancies (V _o) may play a major role in the room temperature magnetism of the Cu-doped ZnO samples.     

Structural and optical properties of monodispersed ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles

Excellent luminescence properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanocrystallites synthesized through a simple chemical method at room temperature are reported. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV–visible absorption and photoluminescence techniques were used to characterize the undoped ZnS, CdS and ZnO and the novel ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles. The optical properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles reflect a combinational effect of the photoluminescent properties of ZnS, CdS and ZnO.     

A study on morphology control and optical properties of ZnO nanorods synthesized by microwave heating

In this study, we present morphology control investigations on zinc oxide (ZnO) nanorods synthesized by microwave heating of a mixture of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) precursors in deionized water (DI water). To study the morphology and structural variations of the obtained ZnO nanorods in different molar ratio of zinc nitrate hexahydrate to HMTA, X-ray diffraction (XRD), scanning electron microscopy (SEM) images, Raman scattering, and photoluminescence (PL) spectroscopy were measured. XRD and SEM images are utilized to examine the crystalline quality as well as the morphological properties of the ZnO nanorods. It is found that morphology control can be achieved by simply adjusting the reactant concentrations and the molar ratio of zinc nitrate hexahydrate to HMTA. Raman scattering and PL spectroscopy measurements were demonstrated to study the size- and shape-dependent optical response of the ZnO nanorods. The Raman scattering result shows that the intensity of LO mode at around 576 cm^?1 decreases with the increase in the molar ratio of zinc nitrate hexahydrate to HMTA, indicating the reduction of defect concentrations in the synthesized ZnO nanorods. Room temperature PL spectrum of the synthesized ZnO nanorods reveals an ultraviolet (UV) emission peak and a broad visible emission. An enhancement of UV emission appears in the PL spectra as the molar ratio of zinc nitrate hexahydrate to HMTA increases, indicating that the defect concentration of the synthesized ZnO nanorods can be reduced by increasing the molar ratio.     

Investigation of Cu Doping,Morphology and Annealing Effects on Structural and Optical Properties of ZnO:Dy Nanostructures

Dysprosium (Dy) doped ZnO nanosheets and nanorods were synthesized by hydrothermal method. Effects of Cu doping, morphology and annealing in Oxygen ambient on structural and optical properties of ZnO nanostructures were investigated using X–ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectra (DRS) and photoluminescence (PL) spectroscopy. This study recommends that both of intrinsic and extrinsic defects facilitate energy transfer (ET) from the ZnO host to Dy³⁺ ions and consequently have an effective role on producing intense Dy emissions at indirect excitation. The results also revealed that annealing process improved the crystal structure of ZnO nanorods due to decrease of surface; however decreased ET and Dy emissions because of diminishing in oxygen vacancy. In addition, as a result of increasing of surface area in nanorods compared to nanosheets, the oxygen vacancies and ET were enhanced. Moreover the results exhibited that electrical and optical properties of ZnO:Dy can be tuned by various amount of Dy concentrations and also Cu doping.     

Effect of some amines,dodecylamine (DDA) and hexadecyldimethylamine (DMHA), on the formation of ZnO nanorods synthesized by hydrothermal route

In this paper, we try to study the effect of two different ionic and nonionic amines dodecylamine (DDA) and hexadecyldimethylamine (DMHA) considered as weak bases and surfactant on the growth of ZnO nanorods using hydrothermal synthesis technique. The self-assembly of oriented attachment (OA) of ZnO nano- and microrods has been successfully obtained by this technique at temperatures greater than 150?°C. The ZnO nano/microrods were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman scattering spectroscopy, Fourier transform infrared (FTIR) and photoluminescence. The XRD measurements show that ZnO prepared by DDA amine presents small grain size in comparison to ZnO obtained from DMHA amine. From SEM characterization, we show that DDA amine has a great effect on the OA of several homogenous ZnO microrods building blocks. The growth process is explained by the formation of ZnO OA in microstructures scale which is depending on ionic character of amines. Optic measurements (Raman, FTIR and photoluminescence) are presented and commented.     

Enhanced photocatalytic activity of Cu-doped ZnO nanorods

Cu-doped ZnO nanorods with different Cu concentrations were synthesized through the vapor transport method. The synthesized nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and UV–vis spectroscopy. The XRD results revealed that Cu was successfully doped into ZnO lattice. The FE-SEM images showed that the undoped ZnO has needle like morphology whereas Cu-doped ZnO samples have rod like morphology with an average diameter and length of 60–90 nm and 1.5–3 μm respectively. The red shift in band edge absorption peak in UV-vis absorbance spectrum with increasing Cu content also confirm the doping of Cu in ZnO nanorods. The photocatalytic activity of pure and Cu-doped ZnO samples was studied by the photodegradation of resazurin (Rz) dye. Both pure ZnO and the Cu-doped ZnO nanorods effectively removed the Rz in a short time. This photodegradation of Rz followed the pseudo-first-order reaction kinetics. ZnO nanorods with increasing Cu doping exhibit enhanced photocatalytic activity. The pseudo-first-order reaction rate constant for 15 % Cu-doped ZnO is equal to 10.17×10^?2min^?1 about double of that with pure ZnO. The increased photocatalytic activity of Cu-doped ZnO is attributed to intrinsic oxygen vacancies due to high surface to volume ratio in nanorods and extrinsic defect due to Cu doping.     

The effect of pre-annealing of sputtered ZnO seed layers on growth of ZnO nanorods through a hydrothermal method

Oriented ZnO nanorods were grown on ion-beam-sputtered ZnO seed layers through a hydrothermal approach without any metal catalyst. The sputtered ZnO seed layers were pre-annealed at different temperatures before the growth of ZnO nanorods. The effects of pre-annealing of the ZnO seed layers on the growth rate, crystallinity and optical properties of ZnO nanorods thereon were studied. The obtained ZnO nanorods had a wurtzite structure and grew along the preferential [0001] orientation with a normal direction to the substrates. Results show that the growth rate and density of the ZnO nanorods strongly depend on the pre-treatment conditions of the ZnO seed layer. With higher pre-treatment temperature, the crystallinity and surface characteristics of the ZnO seed layer were improved and thereafter the growth rate of ZnO nanorods thereon increased. Photoluminescence spectroscopy results show that the UV emission also becomes stronger and sharper with increasing annealing temperature of the ZnO seed layer.     

退火对ZnO薄膜光学特性的影响

用射频磁控溅射法在蓝宝石衬底上制备出ZnO薄膜,通过X射线衍射(XRD)、扫描电镜(SEM)和光致发光(PL)谱等研究了退火温度对ZnO薄膜结构和光学性质的影响。测量结果显示,所制备的ZnO薄膜为六角纤锌矿结构,具有沿c轴的择优取向;随着退火温度的升高,(002)XRD峰强度和平均晶粒尺寸增大,(002)XRD峰半高宽(FWHM)减小,光致发光紫外峰强度增强。结果证明,用射频磁控溅射法通过适当控制退火温度可得到高质量ZnO薄膜。     

Photoluminescence and field emission of 1D ZnO nanorods fabricated by thermal evaporation

Four kinds of new one-dimensional nanostructures, celery-shaped nanorods, needle-shaped nanorods, twist fold-shaped nanorods, and awl-shaped nanorods of ZnO, have been grown on single silicon substrates by an Au catalyst assisted thermal evaporation of ZnO and active carbon powders. The morphology and structure of the prepared nanorods are determined on the basis of field-emission scanning electron microscopy (FESEM) and x-ray diffraction (XRD). The photoluminescence spectra (PL) analysis noted that UV emission band is the band-to-band emission peak and the emission bands in the visible range are attributed to the oxygen vacancies, Zn interstitials, or impurities. The field-emission properties of four kinds of ZnO nanorods have been invested and the awl-shaped nanorods of ZnO have preferable characteristics due to the smallest emitter radius on the nanoscale in the tip in comparison with other nanorods. The growth mechanism of the ZnO nanorods can be explained on the basis of the vapor–liquid–solid (VLS) processes.     

The study of structure and optoelectronic properties of ZnS and ZnO films on porous silicon substrates

ZnS and ZnO films were prepared on porous silicon (PS) substrates with the same porosity by pulsed laser deposition (PLD), and the structural, optical and electrical properties of ZnS and ZnO films on PS were investigated at room temperature by X-ray diffraction (XRD), scanning electron microscope (SEM), optical absorption measurement, photoluminescence (PL) and I–V characteristic studies. The prepared ZnS was obtained in the cubic phase along β-ZnS (1 1 1) orientation which showed a perfect match with the earlier report while ZnO films were obtained in c-axis orientation. There appeared some cracks in the surface of ZnS and ZnO films due to the roughness of PS substrates. Luminescence studies of ZnS/PS and ZnO/PS composites indicated room temperature emission in a broad, intense, visible photoluminescence band, which cover the blue emission to red emission, exhibiting intensively white light emission. Based on the I–V characteristic, ZnS/PS heterojunction exhibited the rectifying junction behavior, while the I–V characteristic of ZnO/PS heterostructure was different from that of the common diode, whose reverse current was not saturated.     

Characterization and optical property of ZnO nano-, submicro- and microrods synthesized by hydrothermal method on a large-scale

In the present paper, well-dispersed ZnO nano-, submicro- and microrods with hexagonal structure were synthesized by a simple low temperature hydrothermal process from zinc nitrate hexahydrate without using any additional surfactant, organic solvent or catalytic agent. The phase and structural analysis were carried out by X-ray diffraction (XRD), the morphological analysis was carried out by field emission scanning electron microscopy (FESEM) and the optical property was characterized by room-temperature photoluminescence (PL) spectroscopy. The results revealed the high crystal quality of ZnO powder with hexagonal (wurtzite-type) crystal structure and the formation of well-dispersed ZnO nano-, submicro- and microrods with diameters of about 50, 200 and 500 nm, and lengths of 300 nm, 1 μm and 2 μm, respectively, on a large-scale just using the different temperatures. Room-temperature PL spectrum from the ZnO nanorods reveals a strong UV emission peak at about 360 nm and no green emission band at ∼530 nm. The strong UV photoluminescence indicates the good crystallization quality of the ZnO nanorods. Room-temperature PL spectra from the ZnO submicro- and microrods reveal a weak UV emission peak at ∼400 nm and a very strong visible green emission at 530 nm, that is ascribed to the transition between V_oZn_i and valence band.     

ZnO–ZnS heterostructures with enhanced optical and photocatalytic properties

ZnO–ZnS heterostructures were fabricated via using ZnO rods as template in different Na₂S aqueous solutions. These heterostructures are 5–6 μm in length and formed by coating ZnO rod with a layer of porous ZnS shell comprising primary crystals about 10 nm in diameter. Subsequently, intact ZnS polycrystalline tubes were obtained by removing the ZnO cores with 25% (wt) ammonia. The as-prepared products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDX), Fourier transform infrared (FT-IR), and electrochemical impedance spectroscopy (EIS). It was found that the electron transfer between ZnS shell and ZnO core strongly affect the photoluminescence and photocatalytic performances of these heterostructures. The rapid transfer of photo-induced electrons from the ZnS shell to the ZnO core leads to enhanced ultraviolet emission. However, if this correlation was destroyed, then the corresponding heterostructure exhibits improved photocatalytic efficiency due to the reduced volume recombination of the charge carries and the multiple reflection effect. Finally, a model based on band-gap alignment was proposed to elucidate the underlying mechanism of the enhanced UV emission and photocatalytic activity of these unique heterostructures.     

The Influence of the Spatial Orientation of ZnO Nanorods on the Luminescence Spectrum

Zinc oxide (ZnO) nanorods were grown on glass substrates coated with a conducting indium tin oxide film using the hydrothermal method. The nanorods are 2–2.5 μm long and 70–200 nm in diameter. Under UV irradiation the nanorods exhibit photoluminescence with a maximum at 382 nm. It is found that changes in angle between the nanorods growth direction and the emission recording direction give rise to an appearance of a violet emission band centered at ～400 nm. It is possible dependence of the luminescence spectrum on the ZnO nanorods’ spatial orientation is due to localization of the violet emission centers in the surface layer.     

Studies on structural and magnetic properties of Co-doped pyramidal ZnO nanorods synthesized by solution growth technique

Large-area arrays of highly oriented Co-doped ZnO nanorods with pyramidal hexagonal structure are grown on silica substrates by wet chemical decomposition of zinc–amino complex in an aqueous medium. In case of undoped ZnO with an equi-molar ratio of Zn²⁺/hexamethylenetetramine (HMT), highly crystalline nanorods were obtained, whereas for Co-doped ZnO, good quality nanorods were formed at a higher Zn²⁺/HMT molar ratio of 4:1. Scanning electron microscope (SEM) studies show the growth of hexagonal-shaped nanorods in a direction nearly perpendicular to the substrate surface with a tip size of ～50 nm and aspect ratio around 10. The XRD studies show the formation of hexagonal phase pure ZnO with c-axis preferred orientation. The doping of Co ions in ZnO nanorods was confirmed by observation of absorption bands at 658, 617 and 566 nm in the UV–vis spectra of the samples. The optical studies also suggest Co ions to be present both in +2 and +3 oxidation states. From the photoluminescence studies, a defect-related emission is observed in an undoped sample of ZnO at 567 nm. This emission is significantly quenched in Co-doped ZnO samples. Further, the Co-doped nanorods have been found to show ferromagnetic behavior at room temperature from vibrating sample magnetometer (VSM) studies.     

退火温度对ZnO薄膜结构和发光特性的影响

采用反应射频磁控溅射法在 Si(100)基片上制备了高c轴择优取向的ZnO薄膜，研究了退火温度对ZnO薄膜的晶粒尺度、应力状态、成分和发光光谱的影响，探讨了ZnO薄膜的紫外发光光谱和可见发光光谱与薄膜的微观状态之间的关系.研究结果显示,在600—1000℃退火温度范围内，退火对薄膜的织构取向的影响较小，但薄膜的应力状态和成分有比较明显的变化.室温下光致发光光谱分析发现，薄膜的近紫外光谱特征与薄膜的晶粒尺度和缺陷状态之间存在着明显的对应关系；而近紫外光谱随退火温度升高所呈现的整体峰位红移是各激子峰相对比例变 关键词： ZnO薄膜 退火 光致发光 射频反应磁控溅射 可见光发射