Effect of pyrolysis temperature on structural,microstructural and optical properties of nanocrystalline ZnO powders synthesised by ultrasonic spray pyrolysis technique

In this article, we report on the effect of pyrolysis temperature on structural, microstructural and optical properties of nanocrystalline ZnO powder synthesised by ultrasonic spray pyrolysis (USP) technique. Powder samples P1, P2 and P3 were prepared at various pyrolysis temperatures (temperature of 2nd zone) of 973, 1073 and 1273?K, respectively. Phases were identified and crystallite sizes were calculated from X-ray diffraction (XRD) diagrams. The morphology and size of ZnO nanocrystallites associated with nanopowder were studied using transmission electron micrograph (TEM). It revealed that the powder consisted of crystallites ranging in size from 9 to 20?nm. These values were matching with the crystallite sizes calculated from XRD. Both XRD and TEM studies of ZnO nanopowders showed that the crystallite sizes increased with an increase in the pyrolysis temperature. The synthesised nanopowders exhibited direct band gap (E _g) in the range 3.37–3.40?eV.     

Synthesis and optical characteristics of ZnO nanocrystals

Zinc oxide nanomaterials with an average particle size of 20–30 nm are readily synthesized by the reaction of zinc acetate and oxalic acid under hydrothermal conditions. The samples are characterized by XRD, SEM, TEM, UV and photoluminescence (PL) studies. The average crystal size of the as prepared ZnO nanopowder is determined by XRD and the values are in good agreement with the TEM analysis. UV absorption spectra revealed the absorption at wavelength < 370 nm indicating the smaller size of ZnO nanoparticles. The quality and purity of ZnO nanomaterial crystalline samples are confirmed by photoluminescence spectra.     

Investigation of annealing-treatment on structural and optical properties of sol-gel-derived zinc oxide thin films

The transparent ZnO thin films were prepared on Si(100) substrates by the sol-gel method. The structural and optical properties of ZnO thin films, submitted to an annealing treatment in the 400–700°C ranges are studied by X-ray diffraction (XRD) and UV-visible spectroscopic ellipsometry (SE). XRD measurements show that all the films are crystallized in the hexagonal wurtzite phase and present a random orientation. Three prominent peaks, corresponding to the (100) phase (2θ ≈ 31.8°), (002) phase (2θ ≈ 34.5°), and (110) phase (2θ ≈ 36.3°) appear on the diffractograms. The crystallite size increases with increasing annealing temperature. These modifications influence the optical properties. The optical constants and thickness of the films have been determined by analysing the SE spectra. The optical bandgap has been determined from the extinction coefficient. We found that the refractive index and the extinction coefficient increase with increasing annealing temperature. The optical bandgap energy decreases with increasing annealing temperature. These mean that the optical quality of ZnO films is improved by annealing.     

沉积气压对电弧离子镀制备ZnO薄膜的结构和性能影响

采用阴极真空电弧离子镀技术在玻璃衬底上制备出了具有择优取向的透明ZnO薄膜. 利用X射线衍射仪、扫描电子显微镜及紫外-可见吸收光谱仪分别对ZnO薄膜的结构、表面形貌及可见光透过率进行了分析.XRD结果表明,所制备的ZnO薄膜具有六角纤锌矿结构的(002)和(101)两种取向,在沉积气压＞1.0Pa时所制备的ZnO薄膜具有(002)择优取向,并且非常稳定.SEM图表明,ZnO晶粒大小较为均匀,晶粒尺寸随着气压升高而变小.在400～1000nm范围内,ZnO薄膜的可见光透过率超过80%,吸收边在370nm附近,所对应的光学带隙约为3.33～3.40eV,并随着沉积气压上升而变大.     

Structure–property correlation of pure and Sn-doped ZnO nanocrystalline materials prepared by co-precipitation

The structural, optical and electrical properties of pure and tin (Sn) doped zinc oxide (ZnO) nanocrystalline materials prepared by co-precipitation method have been studied as a function of Sn doping concentration. The phase identification through powder X-ray diffraction methods confirmed that pure and Sn-doped zinc oxide powder have typical hexagonal wurtzite structure (a = 3.407 Å and c = 4.592 Å) with slight change in lattice parameters. The surface morphological examination with field emission scanning electron microscopy revealed the fact that the grains are closely and densely packed and pores/voids between the grains decrease with increasing the doping concentration of Sn from 0% to 15%. The energy bandgap of pure ZnO was found to be 3.35 eV from optical absorption spectra obtained by ultraviolet–visible (UV–Vis) absorption spectrophotometer. The variation of energy bandgap and electrical resistivity of Sn-doped ZnO were also determined with tin doping. Upon increasing the Sn dopant concentration from 0 to 15 wt%, the optical bandgaps of ZnO increases from 3.35 to 3.42 eV. The electrical resistivity of Sn-doped ZnO has been decreased at least two orders of magnitude, i.e. from 1263.17 to 28.64 Ω cm. This decrement in electrical resistivity may be due to the partial substitution of divalent Zn²⁺ ions with tetravalent Sn⁴⁺ ions, generating more free electrons for conduction.     

Dopant induced bandgap narrowing in Y-doped zinc oxide nanostructures

In this report, hydrothermal synthesis and the absorption properties of the cubic shaped zinc oxide nanostructures doped with different amount of yttrium (Y) metal cation (0 to 15 at.%) are demonstrated. The structural and optical properties of chemically synthesized pure and Y doped ZnO powders are investigated by using powder X-ray diffraction (XRD), field emission scanning electron spectroscopy (FESEM) and transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorbance, photoluminescence (PL), and Fourier transform infra-red spectroscopy (FT-IR). It is found that the dopant ions stabilize in wurtzite hexagonal phase of ZnO upto the concentration of less than 6 at.%, which is mainly due to the fact that the ZnO lattice expands and the optical bandgap energy decreases at this level. Increasing the dopant concentration to greater than 6 at.% leads to a contraction of the lattice, which in turn produces a significant structural disorder evidenced by shift in the XRD peaks due to additional interstitial incorporation of Y. The vibrational modes of the metal oxide groups have been identified from the IR transmission spectra. The optical absorption results show that the optical bandgap energy of Y:ZnO nanocrystals is much less as compared to that of the pure bulk ZnO particles. Doping ZnO with trivalent Y produces excess number of electrons in the conduction band and thus, shifts the absorption edge and narrows down to 80 meV approximately. PL spectra are used to study the dependence of doping on the deep-level emission, which show an enhanced blue emission after Y doping. The existence of near band edge (NBE) emission and blue emission, related to zinc interstitials are observed in the luminescence spectra of Zn(1-x)Y(x)O nanostructures.     

Synthesis of nanosized ZnO by high frequency induction method

In this study, presents an innovative method for nanoparticle synthesis system for nanosized ZnO fabrication with powder or suspension type. The experimental device is primarily composed of a high frequency induction heating system, a pressure control system, a temperature control system and an automatic nanoparticle collection system. This study employs an automatic collection system with liquid nitrogen to condense and collect the nanoparticles. The influence of such process variables such as heating temperature and vacuum pressure are analyzed and compared through experimentation in order to identify the working conditions most conducive to the production of nanoparticles with smaller mean particle size. The prepared ZnO nanoparticles are characterized for nanostructural properties by the TEM and XRD. An Ultraviolet-Visible (UV-Vis) spectrophotometer is used to analyze the optical property of the nanoparticles. The ZnO nanofluid already has good dispersion, so even without dispersant, it can still remain in stable suspension for a fairly long time. Experimental results indicate that the particle size of produced ZnO nanoparticles is around 20 nm and with the production rate of 1.24 g/min.     

Sonochemical assisted synthesis and spectroscopic characterization of Fe3+ doped ZnO diluted magnetic semiconductor

Fe³⁺ doped ZnO nanopowder has been synthesized by sonochemical assistance and characterized by different spectroscopic techniques. The structure, surface morphologies and optical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectrometer (PL) and ultraviolet–visible spectrophotometer. XRD reveals that Fe³⁺ ions enter into ZnO lattices without any secondary phases. SEM micrographs of prepared sample show that surface is rough and stone like structure with different sizes. PL studies of Fe³⁺ doped ZnO nanopowder exhibits ultraviolet and blue emission bands. Magnetometric measurements (vibrating sample magnetometer) indicate ferromagnetic behavior at room temperature. This observation is further confirmed by the EPR spectrum of Fe³⁺ doped ZnO at room temperature.     

Influence of synthetic parameters on the enhanced photocatalytic properties of ZnO nanoparticles for the degradation of organic dyes: a green approach

Herein, we report a green synthetic strategy using aqueous leaves extract of Actinodaphne madraspatna Bedd (AMB) for the synthesis of ZnO NPs. The physical shape, size, thermal stability, surface area, surface composition and chemical state, morphological and optical properties of the synthesized ZnO NPs are well characterized through UV–Visible diffuse reflectance spectroscopy (DRS UV), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis–differential thermal analysis (TGA–DTA), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) and X-ray photon spectroscopy (XPS). FT-IR spectrum of ZnO NPs showed a characteristic peak at 416.62 cm^?1. Optical studies of prepared ZnO NPs showed the bandgap values are reduced in the range of 3.05 to 2.96 eV. The XRD and TEM data revealed the synthesized ZnO NPs exist in wurtzite crystal structure with crystallite sizes of 18 nm to 68 nm range. The variation in bandgap, surface area and crystallite structure of ZnO NPs would be achieved by changing the experimental parameters. FESEM showed spherical-shaped structure. XPS result confirmed the atomic states of Zn and O. The green synthesized ZnO NPs were examined for the photocatalytic degradation of methylene blue (MB) and acid violet 17 (AV17) dyes under UV light and the rate constants ‘k’ was calculated. It is found that the green synthesized ZnO NPs with reduced bandgap showed enhanced photocatalytic activity with higher rate constant.

     

ZnO micro and nanocrystals with enhanced visible light absorption

In this paper, we investigate the effect of the particle size and morphology on the optical properties of ZnO. A series of ZnO micro and nanocrystals were synthesized by the hydrothermal processing of zinc acetate dihydrate and sodium hydroxide as the starting materials, and polyvinylpyrrolidone (PVP) as the polymer surfactant. The particle size and morphology were tailored by adjusting the reactant molar ratios [Zn²⁺]/[OH⁻], while the reaction temperature and the time remained unchanged. X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and high-resolution TEM (HRTEM) have shown that the micro and nanocrystals have a high crystalline pure wurtzite-type hexagonal structure with nanosized crystallites. The size and morphology of the ZnO micro and nanocrystals were investigated by field emission scanning electron microscopy (FE-SEM), which showed a modification from micro-rods via hexagonal-faceted prismatic morphology to nanospheres, caused by simple adjustment of the reactant molar ratio [Zn²⁺]/[OH⁻] from 1:1 to 1:5. The optical properties of the ZnO micro and nanocrystals, as well as their dependence on the particle size and morphology were investigated by Raman and ultraviolet–visible (UV–vis) diffuse reflectance spectroscopy (DRS). The UV–vis spectra showed that the modification of the particle size and morphology from nanospheres to micro-rods resulted in increased absorption, and a slight red-shift of the absorption edge (0.06 eV). Besides, the band gap energy of the synthesized ZnO micro and nanocrystals showed the red shift (∼0.20 eV) compared to bulk ZnO. According to the results of a Raman spectroscopy, the enhanced visible light absorption of the ZnO micro and nanocrystals is related to two phenomena: (1) the existence of lattice defects (oxygen vacancies and zinc interstitials), and (2) the particle surface sensitization by PVP.     

机械化学法一步合成表面改性氧化锌纳米粉体

以醋酸锌、氢氧化钠、硬脂酸为原料,采用机械化学法,一步制备出具有表面亲油性能的氧化锌粉体。借助XRD、FTIR、TEM、纳米粒度测试等方法对粉体进行了表征,研究了硬脂酸对氧化锌粉体表面改性的机理。结果表明,硬脂酸中的羧基与氧化锌颗粒表面的羟基发生了酯化反应,并在表面形成有机膜,氧化锌粉末由亲水性转化为亲油性。当球磨时间为50 min、硬脂酸加入量为氧化锌质量的4.5%时,可以得到平均粒度为90 nm的亲油性氧化锌粉体。     

Influence of annealing on structural, morphological and optical properties of Cd x Zn1?x O nanopowder prepared by Co-precipitation method

Structural and optical properties of Cd _x Zn_1?x O (x = 0.0, 0.025, 0.050, 0.075, 0.1) nanopowder, synthesized by co-precipitation method have been investigated. The effect of annealing on the structural and morphological properties was studied using X-ray diffraction. The samples with x = 0.0 up to 0.075 exhibit wurtzite hexagonal phase, whereas, the sample with x = 0.1 shows two phases: wurtzite hexagonal ZnO and cubic CdO phase. This behavior is explained on the basis of solubility of CdO in ZnO. Energy Dispersive X-ray analysis (EDX) results revealed the existence of Cd, Zn, and O elements in the nanopowder. Transmission Electron Microscopy (TEM) images confirm that the particle size of the prepared samples is in nano range. The optical band gap values obtained from the absorption spectra show that absorption depends on Cd composition. By doping of ZnO with CdO, a red shift in the absorption edge was observed.     

Vacuum annealing of nanocrystalline WC powders

The effect of vacuum annealing temperature on the chemical and phase compositions, particle size, and lattice strain of nanocrystalline tungsten carbide (WC) powders with a particle size from 20 to 60 nm has been studied by X-ray diffraction and electron microscopy. The results demonstrate that vacuum annealing of WC nanopowders at t _ann ≤ 1400°C is accompanied by a marked decrease in carbon content and changes in phase composition due to carbon desorption from the surface of the powder as a result of the interaction of carbon with oxygen impurities. In addition, annealing leads to an increase in particle size due to coalescence of aggregated nanoparticles and reduces the lattice strain of the powder.     

Dielectric investigations of pristine and modified ZnO nanoparticles for energy storage devices

Pristine ZnO, Al-doped ZnO, and TiO₂ coated ZnO nanoparticles (NPs) were synthesized by the wet chemical precipitation technique. All the synthesized NPs were characterized using X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy. XRD analysis of pristine ZnO and Al-doped ZnO NPs revealed the hexagonal wurtzite structure with P6₃mc space group with no secondary phases and impurities. FESEM micrographs also depicted hexagonal grains with well-defined grain boundaries. TEM images showed hexagonal polyhedral shape for pure ZnO NPs and spherical shape dominating polyhedral particle for Al-doped ZnO NPs, and pseudospherical particles for TiO₂ coated ZnO NPs. Energy-dispersive X-ray spectroscopy of Al-doped ZnO indicates the eminent exchange of dopant in the lattice site of Zn. Dielectric Studies reveal the highest value of the dielectric constant and lowest value of dielectric loss for Al-doped ZnO as compared to pure and TiO₂-coated ZnO NPs. Suggesting Al-doped ZnO to be used as a dielectric material that can serve as a basic building block of the energy storage devices such as dielectric capacitor. TiO₂-coated ZnO NPs demonstrated higher AC conductivity in comparison to pure ZnO and Al-doped ZnO NPs suggesting their use as a conductive nanofiller materials in a polymer-based nanocomposite to achieve higher energy density.

     

Structural and Optical Properties of Co-Doped ZnO Thin Films

Co-doped zinc oxide thin films (Zn_1–xCo_xO) have been deposited on c-plane sapphire substrates by dual-beam pulsed laser deposition. The films have lattice parameters similar to that of ZnO, and the lattice parameters are closely distributed. The films grew along a preferred direction, following the epitaxial relationship Zn_1–xCo_xO (0001)substrate (0001). Excitonic emission was suppressed at higher Co-dopant concentration in ZnO because of increase in the distortion of host lattice and defects. When more Zn is replaced by Co, more impurity levels are developed within the bandgap, and more defect are generated. Under our experimental conditions, the bandgap of the films tends to increase with increasing dopant concentration.     

Synthesis, elaboration and characterization of the new material CuIn3S5 thin films

CuIn₃S₅ compound was prepared by direct reaction of high-purity elemental copper, indium and sulphur. CuIn₃S₅ thin films were prepared from powder by thermal evaporation under vacuum (10⁻⁶ mbar) onto glass substrates. The glass substrates were heated from 30 to 200 °C. The powder was characterized for their structural and compositional properties by using X-ray diffraction (XRD) and energy dispersive X-ray (EDAX). The XRD studies revealed that the powder exhibiting P-chalcopyrite structure. From the XRD data, we calculated the lattice parameters a and c. Then, the cation–anion bond lengths l _AC and l _BC are deduced. The films were characterized for their structural, compositional, morphological and optical properties by using XRD, EDAX, atomic force microscopy and optical measurement techniques (transmittance and reflectance). XRD analysis revealed that the films deposited at a room temperature (30 °C) are amorphous in nature, whereas those deposited on heated substrates (≥75 °C) were polycrystalline with a preferred orientation along (112) of the chalcopyrite phase. The surface morphological analysis revealed that the films grown at different substrate temperature had an average roughness between 1.1 and 4.8 nm. From the analysis of the transmission and reflection data, the values of direct and indirect band gap of the films were determined. We found that the optical band gap decreases when the substrate temperature increases.     

Experimental Revelation of Surface and Bulk Lattices in Faceted Cu2O Crystals

Semiconductor crystals have generally shown facet-dependent electrical, photocatalytic, and optical properties. These phenomena have been proposed to result from the presence of a surface layer with bond-level deviations. To provide experimental evidence of this structural feature, synchrotron X-ray sources are used to obtain X-ray diffraction (XRD) patterns of polyhedral cuprous oxide crystals. Cu₂O rhombic dodecahedra display two distinct cell constants from peak splitting. Peak disappearance during slow Cu₂O reduction to Cu with ammonia borane differentiates bulk and surface layer lattices. Cubes and octahedra also show two peak components, while diffraction peaks of cuboctahedra are comprised of three components. Temperature-varying lattice changes in the bulk and surface regions also show shape dependence. From transmission electron microscopy (TEM) images, slight plane spacing deviations in surface and inner crystal regions are measured. Image processing provides visualization of the surface layer with depths of about 1.5–4 nm giving dashed lattice points instead of dots from atomic position deviations. Close TEM examination reveals considerable variation in lattice spot size and shape for different particle morphologies, explaining why facet-dependent properties are emerged. Raman spectrum reflects the large bulk and surface lattice difference in rhombic dodecahedra. Surface lattice difference can change the particle bandgap.     

Deposition of nanocrystalline ZnO by wire explosion technique and characterization of the films' properties

ZnO films deposited on glass, quartz and Al on silicon mono-crystal Si (100) substrates by using the wire explosion technique were investigated by X-ray diffraction (XRD), UV–VIS spectroscopy, scanning electron (SEM) and atomic force microscopy (AFM) measurements. X-ray diffraction measurements have shown that ZnO films are mainly composed of (100), (002) and (101) orientation crystallites. The post-deposition thermal treatment at 600 °C temperature in air has shown that the composite of Zn/ZnO film was fully oxidized to ZnO film. The XRD spectra of the film deposited in oxygen atmosphere at room temperature present high intensity dominating peak at 2h = 36, 32° corresponding to the (101) ZnO diffraction peak. The small fraction of the film (7%) corresponds to the (002) peak intensity at 2h = 34, 42°. This result indicates the good crystal quality of the film and hexagonal wurtzite-type structure deposited by zinc wire explosion. The optical absorption spectra shows the bands at 374, 373 and 371 nm corresponding to deposition conditions. The SEM analysis shows that ZnO films presented different morphologies from fractal network to porous films depending on deposition conditions. AFM analysis revealed the grain size ranges from 50 nm to 500 nm. The nanoneedles up to 300 nm in length were found as typical structures in the film. It was demonstrated that the wire explosion technique is a feasible method to produce ZnO crystalline thin films and nanostructures.     

Hemocompatibility of ZnO thin films prepared by filtered cathodic vacuum arc deposition

Zinc Oxide (ZnO) thin films were prepared by cathodic vacuum arc deposition (CVAD) and filtered cathodic vacuum arc deposition (FCVAD) technology with a mixture of O₂, Ar and N₂. XRD patterns indicated that ZnO thin films prepared by CVAD had a combined orientation of ZnO (002) and ZnO (101). The preferential orientation ZnO (002) could be obtained at an optimum deposition pressure. On the other hand, a perfectly oriented ZnO (002) thin film prepared by FCVAD was obtained in lower pressure, which was beneficial to enhance the crystallization. The wetting behavior showed that all the ZnO thin films prepared by FCVAD were hydrophobic with low surface energy, but the reference samples of the polyurethane (PU) and glass are hydrophilic. Platelet adhesion test indicated that fewer platelets adhered and aggregated on the ZnO thin films prepared by FCVAD. The mechanism of hemocompatibility of ZnO thin films has also been investigated. It is suggested that hydrophobic surface with lower polar component and adhesive work are the two factors responsible for the excellent hemocompatibility.     

Study of Influence of Annealing Time on Some Physical Properties of ZnO:Cu Nanorods Grown by a Simple Chemical Bath Deposition Method

A simple chemical bath deposition method was used to prepare high density ZnO nanorods on ZnO seeded Si substrates. Upon the nanorods growth, Cu-doping was achieved by diffusion process at 500 ^°C for different times in vacuum ambient. The structural, optical, and magnetic properties of the obtained ZnO:Cu nanorods were then examined. XRD analysis showed that undoped and ZnO:Cu samples were highly c-axis oriented with a hexagonal wurtzite structure. SEM analysis indicated that ZnO:Cu nanorods had diameters of ～200 nm and lengths of ～1.5 μm. X-ray photoemission spectroscopy demonstrated that Cu was successfully doped into ZnO in a divalent state. Photoluminescence results showed that Cu-doping caused a decrease in the green band intensity of nanorods compared to undoped ZnO. Room temperature magnetic measurements showed that pure ZnO nanorods exhibited ferromagnetism that might be ascribed to defect-induced d⁰ ferromagnetism. All the ZnO:Cu nanorods also showed the room temperature ferromagnetism that was attributed to the bound magnetic polarons (BMPs).