Tuning the aspect ratio of hydrothermally grown ZnO by choice of precursor

Variable aspect ratio (length/diameter), one dimensional ZnO nanostructures are synthesized by reacting Zn²⁺ precursor derived from Zn·Ac₂, Zn·Cl₂ and Zn·(NO₃)₂ under hydrothermal treatment. The growth mechanism illustrating the formation of self-assembling from individual ZnO nanoparticles to rod-like form is explained briefly. XRD reveals that the ZnO obtained from various zinc salts are pure, wurtzite structure, with crystalline hexagonal phase. The qualitative analysis of ZnO formation and morphology of ZnO nanoparticles are estimated from FESEM and TEM micrographs. Strong UV absorption corresponding to the recombination of electron-hole pair is observed and the blue shift absorption obeys the size confinement effect. The extent of absorption relatively varies when the morphology is changed from nano-bundles to individual rod-like ZnO. When electrons are excited at wavelength of 240 nm, a strong near band edge (NBE) emission and surface defects emission are observed in the PL spectra. The broader emission situated in the blue-green region of the visible spectrum, originating from surface oxygen defects, is not observed in ZnO derived from Zn·Ac₂.     

Simple synthesis and spectroscopic studies on cobalt added ZnO nanocrystals

Cobalt doped zinc oxide nanoparticles were prepared through simple wet chemical method. X-ray diffraction studies confirm the prepared particles are in wurtzite structure. Scanning Electron Microscopy studies show the shape and morphology of the particles. To identify the presence of cobalt in ZnO, Energy Dispersive X-ray analysis was done. Optical absorption measurements show the presence of exciton peak at 375 nm. Photoluminescence studies were done with the excitation wavelength of 330 nm, which shows the emission because of exciton recombination and oxygen vacancy.     

Photoconductivity and photoluminescence of ZnO nanoparticles synthesized via co-precipitation method

Photoconductivity and photoluminescence studies of ZnO nanoparticles (NPs) synthesized by co-precipitation method capped with thioglycerol are carried out. The effect of annealing at 300°C is also studied. The transmission electron micrograph (TEM) and X-ray diffraction (XRD) pattern confirm the hexagonal wurtzite structure of ZnO nanoparticles. The UV-vis absorption spectrum of ZnO NPs shows blue shift of absorption peak as compared to bulk ZnO. The photoluminescence (PL) spectra of as-synthesized ZnO NPs show band edge emission as well as blue-green emission. After annealing band edge emission is quenched. Photocurrent is found to vary super linearly at high voltage for both as-synthesized as well as annealed ZnO NPs. Time resolved rise and decay photocurrent spectra are found to exhibit anomalous photoconductivity for as-synthesized as well as annealed ZnO NPs wherein the photocurrent decreases even during steady illumination.     

Synthesis and characterization of doped and undoped ZnO nanostructures.

Zinc oxide (ZnO) nanoparticles have been produced using precipitation methods from ethanolic solution. Rare-earth metal doping was performed, and the effect of lithium codoping on the luminescence properties of the rare-earth doped products was assessed. The resulting particles were characterized using cathodoluminescence and scanning electron microscopy. It was found that lithium significantly enhanced the cathodoluminescence signal from the rare-earth ions, which has been attributed to the increased integration of the rare-earth ions into the ZnO structure. The nanophase ZnO products were also annealed in argon, hydrogen, and oxygen, with hydrogen being the most successful for removing the broad defect emission present in as-grown samples and enhancing the ZnO near band edge emission.     

Diluted magnetic semiconductor properties in Zn<Subscript>1−x</Subscript>Cu<Subscript>x</Subscript>O nanoparticles synthesized by sol gel route

Nanoparticles of ZnO:Cu Diluted Magnetic Semiconductor (DMS) are prepared using sol gel method. The structural, optical and EPR properties of them are investigated. The XRD patterns of them show the formation of polycrystalline and hexagonal wurtzite structure without any secondary phase formation. The average size of particles ranges from 14 to 19 nm. In the optical absorption study of the samples, a red shit of optical band edge and a narrowing of the optical band gap are observed when Cu concentration is increased. The PL measurements illustrate 392 nm UV radiation of the near band-edge emissions of ZnO, blue emission at 450 nm and orange emission at 628 nm. The cause of decrease in intensity of these emission lines is the sincerely enhanced non-radiative transitions when Cu is doped in ZnO. EPR measurements provide substantial evidence for the presence of defect states and enhancement of exchange interaction.     

Structures and optical properties of Zn1?x Ni x O nanoparticles by coprecipitation method

Nanocrystals of undoped and nickel-doped zinc oxide (Zn_1?x Ni _x O, where x?=?0.00?C0.05) were synthesized by the coprecipitation method. Crystalline size, morphology, and optical absorption of prepared samples were determined by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), and UV?Cvisible spectrometer. XRD and SEM studies revealed that Ni-doped ZnO crystallized in hexagonal wurtzite structure. Doping of ZnO with Ni²⁺ was intended to enhance the surface defects of ZnO. The incorporation of Ni²⁺ in place of Zn²⁺ provoked an increase in the size of nanocrystals as compared to undoped ZnO. Crystalline size of nanocrystals varied from 10 to 40?nm as the calcination temperature increased. Enhancement in the optical absorption of Ni-doped ZnO indicated that it can be used as an efficient photocatalyst under visible light irradiation. Optical absorption measurements indicated a red shift in the absorption band edge upon Ni doping. The band gap value of prepared undoped and Ni-doped ZnO nanoparticles decreased as annealing temperature was increased up to 800?°C.     

On the Origin of the Large Stokes-Shift of the Emission of CdS Nanoparticles Embedded in a Phosphate Glass Matrix

XRD and TEM characterisation evidenced the formation of well-dispersed CdS nanoparticles inside a phosphate glass matrix. Optical absorption and time-resolved photoluminescence study were carried out on the prepared glass samples. Optical absorption revealed the fast character of the growth of CdS nanoparticles in this medium. Photoluminescence spectra showed only one large band with a maximum at almost 740 nm, which was associated to transitions between energy levels within the bandgap of the CdS nanoparticles. From the steady state and time-resolved measurements, it was suggested that the emission comes mainly from sulfur vacancies inside the nanocrystals and on its surface, which act as deep traps for the photogenerated electrons. The creation of such vacancies was attributed to the loss of sulfur during the glass preparation as evidenced from a chemical analysis using energy dispersive X-ray spectrometry. These traps may be also induced by the fast growth of CdS nanocrystals in this matrix or laser exposure during PL measurements. These CdS-doped glasses with an intense absorption in the UV–Vis region and a large emission band with long lifetime and a large Stokes-shift are adequate for luminescent solar concentrators, photocatalytic applications and solid-state lasers.     

Structural,optical and photoluminescence properties of Zn<Subscript>1−x</Subscript>Ce<Subscript>x</Subscript>O (x = 0, 0.05 and 0.1) nanoparticles by sol–gel method annealed under Ar atmosphere

Ce doped ZnO nanoparticles (Zn_1−xCe_xO, x = 0.0, 0.05 and 0.1) have been synthesized by sol–gel method at annealing temperature of 500 °C for 1 h under Ar atmosphere. The synthesized samples have been characterized by powder X-ray diffraction (XRD), energy dispersive X-ray studies, UV–Visible spectrophotometer and fourier transform infrared (FTIR) spectroscopy. The XRD measurements indicate that the prepared nanoparticles have a hexagonal wurtzite structure and CeO₂ crystallites. The calculated average crystalline varied from 21.97 to 15.62 nm with increase in Ce concentrations. The increase in lattice parameters reveals the substitution of Ce into ZnO lattice. The presence of functional groups and the chemical bonding is confirmed by FTIR spectra. PL spectra of the Zn_1−xCe_xO system show that the shift in near band edge emission from 386 to 363 nm and a shift in blue band emission from 517 to 485 nm which confirms the substitution of Ce into the ZnO lattice.     

Novel Green Route of Synthesis of ZnO Nanoparticles by Using Natural Biodegradable Polymer and Its Application as a Catalyst for Oxidation of Aldehydes

ZnO nanoparticles have been synthesized by using biodegradable natural biopolymer viz. Gum Tragacanth. This single step approach is very cost effective and reproducible. The reaction time and concentration of precursor zinc acetate play a major role in the nature and growth of ZnO nanoparticles. ZnO nanoparticles were characterized by X-ray diffraction, SEM, FTIR, EDAX, UV-visible spectroscopy and TEM. ZnO nanoparticles with 20-30 nm in diameter and hexagonal morphology were found; dispersed uniformly. Raman spectrum shows the mode E₂ high at 437 cm^?1 that is related to the vibration of wurtzite Zn-O bond in crystal structure of ZnO. The space between adjacent lattice fringes is ～ sharp 2.42 Å. UV-visible absorption spectrum shows the sharp absorption band at 308 nm assigned to the intrinsic transition from valance band to conduction band. The ZnO nanoparticles display superior catalytic activity of conversion of aldehyde to acid as compared to bulk-ZnO material, because of high surface area of ZnO nanoparticles. A trace amount of ZnO nanoparticles catalyst required for organic conversion. The ZnO nanoparticles as catalyst are highly stable, recyclable and efficient in its activity.     

Enhancement of optical conductivity in the ultra-violet region of Cs doped ZnO sol gel thin films

Nano crystalline cesium (Cs) doped ZnO thin films were deposited on glass substrate by sol gel spin coating method with 1–3 mol.% doping concentration and different annealing temperatures. The deposited films were characterized by X-ray diffraction (XRD), Hall Effect, Photoluminescence (PL) and UV–Visible studies. XRD measurements reveal that all the samples abound in the wurtzite structure with polycrystalline nature. An increase in crystalline size from 19.60 to 44.54 nm is observed with the increase of doping concentration. Electrical conductivity of Cs doped ZnO films were observed from Hall effect measurements and the maximum carrier concentration obtained is 7.35 × 10¹⁸ cm^?3. The near band emission (384 nm) peak intensity increases with the increase of Cs doping concentration and a maximum intensity 55,280 was observed for CZ3 film from PL spectrum. Also a low energy near infrared (NIR) emission peak centered at 1.62 eV appears for the Cs doped ZnO films. The average transmission of CZ film is 88 % and the absorption edge is red shifted with the increase of Cs doping concentration and also the optical conductivity increases in the UV region.     

Photocatalytic studies of silver doped ZnO nanoparticles synthesized by chemical precipitation method

Ag-doped ZnO nanoparticles (Zn_1?xAg_xO; where x = 0.00–0.05) were synthesized by chemical precipitation method. The synthesized products were characterized by X-ray diffraction, scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–Vis spectrometer. The SEM and TEM micrographs revealed the agglomerated spherical-like morphology and the measurements show that the size of crystallites is in the range of 10–40 nm. Optical measurements indicated a red shift in the absorption band edge after Ag doping. The band gap values of as prepared undoped and doped with silver samples were found to decrease with increase in temperature from 300 to 800 °C. Photocatalytic activities of ZnO and Ag doped ZnO were evaluated by irradiating the sample solution to ultraviolet light by taking methylene blue as organic dye. The experiment demonstrated that the photo-degradation efficiency of 1 mol% Ag-doped ZnO was significantly higher than that of undoped and 2–5 mol% Ag doped ZnO under ultraviolet light irradiation.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

油分散性氧化锌纳米微粒的制备及表征

采用直接沉淀法制备了异丁酸修饰纳米氧化锌微粒，用XRD、TEM、XPS、IR、UV-Vis、PL等检测手段对样品进行结构表征。结果表明：所制的样品为纤锌矿结构的氧化锌颗粒，粒度约为20 nm，异丁酸分子与表面锌原子以双齿螯合的形式结合。 Zn(II)2p_3/2的结合能与Zn的标准峰位相比，向低结合能方向移动了1.5 eV，其在可见光区比紫外区的荧光发射显著增强。分散性实验表明，样品在有机溶剂中有良好的分散性。     

Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ～343°C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.     

纳米α-Fe~2O~3的XANES研究

选择纳米α-Fe~2O~3体系,运用X射线近边吸收谱(XANES)技术对纳米材料进行分析。结果表明,三种尺寸的纳米α-Fe~2O~3样品(颗粒尺寸分别是3nm,10nm和55nm)与粗颗粒商品的氧K边XANES谱的不同之处在于,纳米样品出现了一个新的吸收B峰。研究揭示,该峰可能是纳米α-Fe~2O~3中晶界部分氧的2p-4sp杂化所产生的一个新电子跃迁末态造成的。进一步的研究表明,随着纳米α-Fe~2O~3的粒子尺寸减小,氧的2p轨道和铁的3d轨道杂化增加,主要体现在2p-e~g杂化程度加剧,使得纳米颗粒中铁周围的氧配位八面体畸变程度加强。最后,通过对3nm样品在研磨和不研磨两种制样方式获得的氧K边XANES谱分析,证实纳米粒子体系中存在特殊的协同作用力。     

Red edge excitation and proton association in the excited state of acridine

A comprehensive study of acridine spectra with variation of pH, wave length of excitation, deuteration of the solvent, etc., has been made. The excited state protonation of acridine is found extra-ordinarily excitation wavelength sensitive near the red edge of the first absorption band. The proton association takes place very fast (K _PT ~ 10¹⁰ sec^-1) on excitation at the red edge of the first absorption band (ree) and acridinium emission is observed while it is slow on short wavelength excitation (swe). The reaction rate slows down at lower temperature which is indicated by a delay in the initiation of the effect by ~ 8 nm on ree. The acridinium type emission with ree at 80 K shows that proton tunnelling is the chief mechanism of proton transfer. The quantum yields are also found wavelength dependent. Contrary to previous observations acridinium ion also shows a ree shift at 80 K.     

Influence of laser irradiation on the optical properties of nano-sized powder of metal oxide

ZnO Nano powders were prepared by co-precipitation method which includes post-oxidation and annealing in air. Influence of laser irradiation was carried out using 355 nm laser on the physical properties of ZnO nanoparticles. SEM studies reveal agglomeration of grains resulting into enlargement and deformation of the nanoparticles. XRD pattern exhibited decrease in FWHM which is a clear evidence of the increase in crystallite size due to laser irradiation. Optical properties showed decrease in the band gap of the laser irradiated Nano powders. The observed results indicated the UV laser irradiation increases the ZnO nanoparticles crystallinity that affects the optical properties of the ZnO.     

Preparation and properties of polymer/zinc oxide nanocomposites using functionalized zinc oxide quantum dots

Poly(methyl methacrylate) (PMMA)/zinc oxide (ZnO) or carbazole polymer (PCEM)/ZnO nanocomposites, which are composed of high molecular weight PMMA or PCEM with narrow molecular weight distributions and ZnO nanoparticles, were successfully prepared by atom transfer radical polymerization (ATRP) initiated by 2-bromo-2-methylpropionyl (BMP) group (ZnBM) introduced onto the ZnO nanoparticle surfaces. Introduction of the BMP group onto the ZnO surfaces was achieved by esterification of OH group of the ZnO surfaces. The chemically attached OH group-having ZnO nanoparticles (ZnHM) were fabricated by sol-gel reaction from zinc acetate dihydrate, followed by treatment of the ZnO nanoparticles with 2-hydroxypropionic acid (HPA). The ZnHM nanoparticles showed one UV absorption and two emission bands: UV emission peak and broad visible emission band, while the ZnBM exhibited broad UV absorption and no emission spectra. The PMMA/ZnO nanocomposites displayed UV absorption and photoluminescent (PL) band with blue emission on the basis of the ZnHM nanoparticles, where the ZnO nanoparticles dispersed homogeneously in the PMMA matrix. The PCEM/ZnO nanocomposites depicted UV emission peak due to the carbazole unit in the UV range, but no visible emission. Thermal properties of the PMMA/ZnO nanocomposites were improved by dispersion of the ZnO nanoparticles into the PMMA, but the PCEM/ZnO nanocomposites showed no improvement of the thermal properties.     

Nearly monodispersed ZnS nanospheres: Synthesis and optical properties

ZnS nanoparticles of diameters of 3–4 nm were self-assembled to form dense nanospheres of sizes 100 nm by a colloidal precipitation method using PVP as the stabilizing agent. Studies indicated that the ZnS nanoparticles maintained their individual properties inside the nanospheres. Optical absorption spectra of the samples demonstrated the effect of quantum confinement in the ZnS nanocrystals. Room temperature photoluminescence measurements showed a sharp UV emission at 370 nm, attributed to sulfur vacancies.     

ZnO/SiO2的激光诱导发光光谱研究

用激光诱导发光光谱技术对一系列不同ZnO担载量的ZnO/SiO2及在不同焙烧气氛下制备的ZnO/SiO2材料进行了深入的研究,发现在空气气氛中焙烧的ZnO/SiO2主要出现ZnO的橙色发光带(中心位于670nm),但在氩气气氛中焙烧制得的样品主要呈现ZnO的绿色发光带(中心位于540nm),且明显观察到橙色发光带和绿色发光带之间的转化.ZnO的可见光区发光带可能是由ZnO中的氧缺陷引起的,高浓度的氧缺陷引发绿色发光带,而低浓度的氧缺陷引发橙色发光带.结果表明,激光诱导发光光谱是一种表征缺陷的有力工具,常规表征技术很难对材料的缺陷状态进行表征.XRD衍射图谱表明,样品中ZnO是以纤锌矿结构存在的,紫外-可见漫反射光谱和拉曼光谱显示,ZnO主要以大颗粒状态覆盖在SiO2表面上.