Local structure and photocatalytic property of sol–gel synthesized ZnO doped with transition metal oxides

ZnO nanoparticles doped with up to 5 at% of Co and Mn were prepared using a co-precipitation method. The location of dopant ions and the effect of doping on the photocatalytic activity were investigated. The crystal structure of nanoparticles and local atomic arrangements around dopant ions were analyzed by X-ray absorption spectroscopy. The results showed that the Co ions substituted the Zn ions in the ZnO wurtzite phase structure and induced lattice shrinkage, while Mn ions were not completely incorporated in the crystal lattice. The photocatalytic activity under simulated sunlight was characterized by the decomposition of Rhodamine B dye molecules. It was revealed that Co-doping strongly reduced the photocatalytic activity but Mn-doping showed a weaker effect on the reduction of the photoactivity.     

Synthesis and alignment of Zn and ZnO nanoparticles by laser-assisted chemical vapor deposition

A simple, versatile, and fast laser-assisted chemical vapor deposition (LCVD) technique that produces linear arrays of Zn and ZnO nanoparticles on a silicon substrate, covering an extended region, is described. A series of consecutive steps is involved in the synthesis and alignment of Zn/ZnO nanoparticles. First, a Lloyd's mirror arrangement is employed to produce two types of periodic nanostructure, i.e., nanoripples and nanoprotrusions. Next, the nanostructured substrate is laser irradiated at a fluence of 60?mJ?cm(-2) in the presence of the metall-organic (MO) precursor gas diethylzinc (DEZn). The evolution of the Zn nanocrystals by LCVD processing was studied as a function of precursor gas pressure and laser fluence by ex situ high-resolution scanning electron microscopy (SEM). Laser irradiation fulfills a double role: it decomposes the adsorbed precursor and causes the evolution of resulting Zn into aligned aggregates of zinc nanoparticles. The Zn nanoparticles react with oxygen upon high-temperature thermal annealing to yield aligned assemblies of ZnO nanoparticles. The production of ZnO was confirmed by x-ray diffraction (XRD) and photoluminescence spectra. This technique is general and could be used in a large number of substrate/precursor combinations.     

ZnO nanoparticles embedded in sapphire fabricated by ion implantation and annealing

ZnO nanoparticles were fabricated in sapphire (α-Al(2)O(3) single crystal) by Zn ion implantation (48?keV) at an ion fluence of 1 × 10(17)?cm(-2) and subsequent thermal annealing in a flowing oxygen atmosphere. Transmission electron microscopy (TEM) analysis revealed that metallic Zn nanoparticles of 3-10?nm in dimensions formed in the as-implanted sample and that ZnO nanoparticles of 10-12?nm in dimensions formed after annealing at 600?°C. A broad absorption band, peaked at 280?nm, appeared in the as-implanted crystal, due to surface plasma resonance (SPR) absorption of metallic Zn nanoparticles. After annealing at 600?°C, ZnO nanoparticles resulted in an exciton absorption peak at 360?nm. The photoluminescence (PL) of the as-implanted sample was very weak when using a He-Cd 325?nm line as the excitation source. However, two emission peaks appeared in the PL spectrum of ZnO nanopraticles, i.e., one ultraviolet (UV) peak at 370?nm and the other a green peak at 500?nm. The emission at 500?nm is stronger and has potential applications in green/blue light-emitting devices.     

Doping effects of Co(2+) ions on ZnO nanorods and their photocatalytic properties

A series of Zn(1-x)Co(x)O nanorods with dopant content ranging from x = 0.00 to 0.10 was prepared by a wet chemical method. All Zn(1-x)Co(x)O samples were investigated by x-ray diffraction, transmission electron microscopy, energy-dispersion x-ray line mapping analysis, and UV-visible absorption spectroscopy. It was found that Co(2+) ions were homogeneously substituted for Zn(2+) ions in ZnO nanorods. Rhodamine B degradation was used as a probe reaction to evaluate the effect of Co(2+) doping on ZnO nanorods and photocatalytic performance under UV light and visible light irradiation. Co(2+) ions acted as the trapping or recombination centers for electrons and holes, leading to a reduction in photodegradation efficiency under UV light illumination. Alternatively, Co(2+) ions enhanced the optical absorption and produced the photoinduced carriers under visible illumination in terms of two charge transfer transitions involving Co(2+) ions. Consequently, Co(2+) ions substituted in the lattice of ZnO nanorods significantly improved the visible light photocatalytic activity.     

氧化锌薄膜的拉曼光谱研究

利用拉曼光谱结合X射线衍射分析对未掺杂和掺杂的ZnO薄膜，陶瓷薄膜进行了研究，ZnO薄膜及ZnO陶瓷薄膜均由sol-gel法制备，掺杂组份有Bi2O3,Sb2O3,MnO和Cr2O3等。结果表明，未掺杂的薄膜的ZnO主晶相均表现出显著的定向生长特征，其拉曼光谱特征谱峰为437cm^-1，谱峰强度随薄膜退火温度的提高略有增强，掺杂后ZnO的拉曼谱峰发生了红移，掺Bi2O3后ZnO的拉曼谱峰由347cm^-1移质移至434cm^-1，掺Sb2O3后ZnO的拉曼谱峰移至435cm^-1，而掺杂Bi2O3,Sb2O3,MnO和Cr2O3等组份的ZnO陶瓷薄膜的ZnO拉曼谱峰则移至434cm^-1，说明掺杂元素进入了ZnO晶格，引起了晶格的变化，ZnO薄膜性能不仅受次晶相组成的影响，而且受因掺杂元素进入而引起的ZnO晶格畸变的影响。     

Chemical conversion synthesis of ZnS shell on ZnO nanowire arrays: morphology evolution and its effect on dye-sensitized solar cell

Heterostructured ZnO/ZnS core/shell nanowire arrays have been successfully fabricated to serve as photoanode for the dye-sensitized solar cells (DSSCs) by a facile two-step approach, combining hydrothermal deposition and liquid-phase chemical conversion process. The morphology evolution of the ZnS coated on the ZnO nanowires and its effect on the performance of the DSSCs were systematically investigated by varying the reaction time during the chemical conversion process. The results show that the compact ZnS shell can effectively promote the photogenerated electrons transfer from the excited dye molecules to the conduction band of the ZnO, simultaneously suppress the recombination for the injected elelctrons from the dye and the redox electrolyte. As reaction time goes by, the surface of the nanowires becomes coarse because of the newly formed ZnS nanoparticles, which will enhance the dye loading, resulting in increment of the short-circuit current density (J(SC)) . Open-circuit photovoltage decay measurements also show that the electron lifetime (τ(n)) in the ZnO/ZnS core/shell nanostructures can be significantly prolonged because of the lower surface trap density in the ZnO after ZnS coating. For the ZnO/ZnS core/shell nanostructures, the J(SC) and η can reach a maximum of 8.38 mA/cm(2) and 1.92% after 6 h conversion time, corresponding to 12- and 16-fold increments of as-synthesized ZnO, respectively.     

机械化学法合成纳米ZnO粉体

利用机械化学法合成了单相ZnO粉体,XRD分析结果表明,ZnSO₄/NaOH(mol比)在1/2.1～1/3.0之间均可合成ZnO粒子,ZnO产率在ZnSO₄/NaOH为1/2.5时最大,TEM分析表明,ZnO粒子的粒径在40～80nm范围,对于反应机理,认为是固-固反应中放出的大量的热,使Zn(OH)₂直接转化为ZnO粒子,光吸收性能表明,纳米ZnO粉体的紫外吸收性能(200～400nm)较普通ZnO粉体强得多。     

A simple solution route to controlled synthesis of ZnS submicrospheres, nanosheets and nanorods

ZnS nanostructures with different morphologies of submicrospheres, nanosheets and nanorods were synthesized by solution precipitation of thiourea with Zn(NO(3))(2) in the presence of block copolymer at low temperature. The sizes and morphologies of ZnS can be controlled simply by?changing the processing parameters. The results show that the ZnS submicrospheres are of 250-500?nm in diameter, nanosheets are 2.5?μm × 5.5?μm with an estimated thickness of 20-30?nm, and nanorods are 2-5?nm in diameter and 10-30?nm in length. Keeping the precursor system in an autoclave at 105?°C results in the formation of ZnS submicrospheres; ultrasonication and keeping the system at room temperature leads to the formation of ZnS nanosheets; and long-time continuous ultrasonication and keeping the system in an autoclave at 105?°C induces the formation of uniform ZnS nanorods. We argue that the reaction temperature and P123 may play crucial roles in the formation of three ZnS structures in this work. The morphologically controllable synthesis strategies may be extended to the shape-controlled production of nanostructures of other inorganic materials.     

Morphology-controlled synthesis of ZnS nanostructures via single-source approaches

ZnS nanoparticles of various morphologies, including hollow or solid spherical, and polyhedral shape, were synthesized from single-source precursor Zn(S₂COC₂H₅)₂ without using a surfactant or template. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy. The results indicate that ZnS hollow and solid spheres assembled by nanoparticles can be easily generated by the solution phase thermalysis of Zn(S₂COC₂H₅)₂ at 80 °C using N, N-dimethylformamide (DMF) and ethylene glycol (EG) or water as solvents, respectively, whereas solvothermal process of the same precursor led to ZnS nanoparticles of polyhedral shape with an average size of 120 nm. The optical properties of these ZnS nanostructures were investigated by room-temperature luminescence and UV-vis diffuse reflectance spectra.     

Core/Shell ZnO/ZnS Nanoparticle Electron Transport Layers Enable Efficient All-Solution-Processed Perovskite Light-Emitting Diodes

Solution-processed perovskite-based light-emitting diodes (PeLEDs) are promising candidates for low-cost, large-area displays, while severe deterioration of the perovskite light-emitting layer occurs during deposition of electron transport layers from solution in an issue. Herein, core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer in PeLED based on quasi-2D PEA₂Cs_n−1Pb_nBr_3n+1 (PEA = phenylethylammonium) perovskite are employed. The deposition of ZnS shell mitigates trap states on ZnO core by anchoring sulfur to oxygen vacancies, and at the same time removes residual hydroxyl groups, which helps to suppress the interfacial trap-assisted non-radiative recombination and the deprotonation reaction between the perovskite layer and ZnO. The core/shell ZnO/ZnS nanoparticles show comparably high electron mobility to pristine ZnO nanoparticles, combined with the reduced energy barrier between the electron transport layer and the perovskite layer, improving the charge injection balance in PeLEDs. As a result, the optimized PeLEDs employing core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer exhibit high peak luminance reaching 32 400 cd m⁻², external quantum efficiency of 10.3%, and 20-fold extended longevity as compared to the devices utilizing ZnO nanoparticles, which represents one of the highest overall performances for solution-processed PeLEDs.     

Effect of inorganic shells on luminescence properties of ZnS:Ag nanoparticles

The hydrothermally synthesized Ag-doped ZnS (ZnS:Ag) nanoparticles have been coated with inorganic shells by a chemical precipitation method. The ZnS:Ag/ZnS, ZnS:Ag/CdS, and ZnS:Ag/ZnO core–shell nanoparticles with different thickness of ZnS, CdS, and ZnO shells have been prepared. The effects of shells on the luminescence properties of ZnS:Ag cores have been investigated through the photoluminescence (PL) spectra and luminescence stabilities of products. In the core–shell nanoparticles involved here, the ZnO shell can most significantly enhance the luminescence of ZnS:Ag cores. The 450 nm emission intensity of ZnS:Ag/ZnO nanoparticles is up to 125 % of that of ZnS:Ag nanoparticles. However, the ZnO shell can hardly influence the luminescence stability under ultraviolet irradiation. The ZnS shell can only increase the luminescence of ZnS:Ag cores to some extent, but it can improve the luminescence stability under ultraviolet irradiation. Although the CdS shell can improve the luminescence stability to some extent, it quenches the luminescence of ZnS:Ag nanoparticles dramatically.     

纳米ZnS/PVDF复合膜的制备及其光学性能

以醋酸锌(ZnAC₂ ·2H₂O)和聚偏氟乙烯(PVDF)为原料, N-N-二甲基甲酰胺为溶剂, 采用溶胶-凝胶原位复合的方法制备纳米硫化锌/聚偏氟乙烯复合膜。X射线衍射和透射电镜分析表明, 复合膜中的ZnS晶粒分布均匀, 平均尺寸在3~7nm之间, 具有明显的立方相结构。紫外-可见吸收光谱和荧光光谱分析表明, 随着ZnS晶粒度的减小, 复合膜的吸收边出现从310→270nm的蓝移, 该复合膜中同时存在368nm的激子复合发光和429nm自激活发光。分散剂的加入不会对复合膜的荧光性能产生本质的影响, 但可以使ZnS生长速度减慢, 分散更均匀。      

Time resolved spectroscopic studies on some nanophosphors

Time resolved spectroscopy is an important tool for studying photophysical processes in phosphors. Present work investigates the steady state and time resolved photoluminescence (PL) spectroscopic characteristics of ZnS, ZnO and (Zn, Mg)O nanophosphors both in powder as well as thin film form. Photoluminescence (PL) of ZnS nanophosphors typically exhibit a purple/blue emission peak termed as self activated (SA) luminescence and emission at different wavelengths arising due to dopant impurities e.g. green emission for ZnS: Cu, orange emission for ZnS: Mn and red emission for ZnS: Eu. The lifetimes obtained from decay curves range from ns to ms level and suggest the radiative recombination path involving donor-acceptor pair recombination or internal electronic transitions of the impurity atom. A series of ZnMgO nanophosphor thin films with varied Zn: Mg ratios were prepared by chemical bath deposition. Photoluminescence (PL) excitation and emission spectra exhibit variations with changing Mg ratio. Luminescence lifetime as short as 10⁻¹⁰ s was observed for ZnO and ZnMgO (100: 10) nanophosphors. With increasing Mg ratio, PL decay shifts into microsecond range. ZnO and ZnMgO alloys up to 50% Mg were prepared as powder by solid state mixing and sintering at high temperature in reducing atmosphere. Time resolved decay of PL indicated lifetime in the microsecond time scale. The novelty of the work lies in clear experimental evidence of dopants (Cu, Mn, Eu and Mg) in the decay process and luminescence life times in II–VI semiconductor nanocrystals of ZnS and ZnO. For ZnS, blue self activated luminescence decays faster than Cu and Mn related emission. For undoped ZnO nanocrystals, PL decay is in the nanosecond range whereas with Mg doping the decay becomes much slower in the microsecond range.     

Enhanced and stable green emission of ZnO nanoparticles by surface segregation of Mg

The effects of Mg addition on the emission of green photons from ZnO nanoparticles were studied. Energy dispersive x-ray spectroscopy (EDS) and Auger electron spectroscopy (AES) data demonstrated that ZnO nanoparticles with surface segregation of MgO (ZnO:MgO) were precipitated from colloidal reactions between Zn(2+),Mg(2+) and OH(-) ions suspended in ethanol. The photoluminescence emission spectra showed stronger green emission from suspended ZnO:MgO versus ZnO nanoparticles. ZnO:MgO also exhibited a stable green emission colour, which was slightly red-shifted from 495 to 520?nm with 168 days of ageing. It was postulated that the presence of MgO on the surface of ZnO prevented both the aggregation of ZnO nanoparticles via electrostatic stabilization of the suspension, and the formation of non-radiative recombination states on the surface, resulting in more intense, stable photoemission from ZnO. The red shift of the green emission from suspended ZnO nanoparticles with extended ageing was attributed to filling of radiative surface trap states in the bandgap.     

Preparation and characterization of ZnO/ZnS core/shell nanocomposites through a simple chemical method

In this paper, we reported the preparation of ZnO/ZnS core/shell nanocomposites by sulfidation of ZnO nanostructures via a simple hydrothermal method. The precursors of bare ZnO nanoparticles and ZnO nanorods were synthesized by a surfactant-assisted hydrothermal growth. The structural, morphological, and element compositional analysis of bare ZnO nanostructures and ZnO/ZnS core/shell nanocomposites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy techniques. The XRD results indicated that the phase of bare ZnO nanoparticles and ZnO nanorods was wurtzite structure, and the phase of coated ZnS nanoparticles on the surface of bare ZnO nanostructures was sphalerite structure with the size of about 8 nm. Photoluminescence measurement was carried out, and the PL spectra of ZnO/ZnS core/shell nanocomposites revealed an enhanced UV emission and a passivated orange emission compared to that of bare ZnO nanostructures. In addition, the growth mechanism of ZnO/ZnS core/shell nanostructures through hydrothermal method was preliminarily discussed.     

Direct synthesis of monodispersed ZnO nanoparticles in an aqueous solution

Monodispersed ZnO nanoparticles with mesopores were successfully prepared via a simple route through the transformation of Zn(NH₃)₄²⁺ precursor in the presence of sodium oleate and hydrazine at 80 °C with the pH of 8.5. Hydrazine and sodium oleate were used to control the size at 30-60 nm and to improve dispersion properties of ZnO nanoparticles. The samples were characterized by TEM, XRD, IR and TG-DTA, and the results suggest that the grains are composed of ZnO and a small quantity of oleate. The oleate plays an important role in preventing the ZnO nanoparticles from aggregating.     

纳米ZnO-γ-Al_2O_3复合粉体的制备及其光催化性能

以γ-Al2O3为载体,采用均相沉淀法制备不同ZnO负载量的纳米ZnO-γ-Al2O3复合粉体。通过X射线粉末衍射(XRD)、扫描电镜(SEM)和氮气吸附对复合粉体的结构、表面形貌和比表面积进行表征。以壬基酚聚氧乙烯醚(NPE-10)为模拟污染物,对复合粉体的光催化性能进行评价。结果表明:ZnO成功负载到了γ-Al2O3表面,且负载量随着ZnO比例的增加而增加,当ZnO与γ-Al2O3质量比为2:1时,ZnO在γ-Al2O3表面形成均匀的薄膜,且这时的复合粉体催化性能最好。煅烧温度、复合物用量对其光催化性能有显著影响,300℃下煅烧所得的复合粉体,当添加量为0.3 g时,在紫外光下照射4 h后降解率可达到96%以上,重复使用6次后降解率仍可达90%以上。     

Thin ZnO nanocomposite poly(styrene–acrylic acid) films on Si and SiO2 surfaces

The properties and formation of self-assembled ZnO nanoclusters using polystyrene-based diblock copolymers are reported. The polystyrene–polyacrylic acid copolymer consisting of a majority block (polystyrene) and a minority block (polyacrylic acid) with a block number average molecular weight ratio of 16,500/4500 and a block repeat unit ratio of 159/63 was used in order to obtain self-assembly due to microphase separation with spherical morphology. The self-assembly of the inorganic nanoparticles was achieved at room temperature in the liquid phase using a ZnCl₂ precursor dopant attached to the minority block, and both dry and wet chemical processing techniques compatible with semiconductor manufacturing were developed in order to convert the ZnCl₂ precursor into ZnO. The polymer films were applied by standard spin-on photolithographic techniques on Si wafers with and without thermally grown SiO₂ surface films. A study by X-ray photoelectron spectroscopy (XPS) confirmed the conversion of the ZnCl₂ dopant precursor into ZnO within the copolymer matrix, and atomic force microscopy (AFM) showed the spherical morphology of the resultant ZnO nanoclusters. Conversion of the precursor into ZnO was achieved both by a wet chemical treatment and by developing a new dry chemical treatment process based on ozone exposure. The study showed that the dry treatment has better stability and shorter conversion exposure times on the Si surfaces than the wet treatment approach, resulting in lateral size distribution between 250 and 350 nm and height distribution between 80 and 130 nm for the ZnO nanoclusters.     

Effect of Fe doping concentration on optical and magnetic properties of ZnO nanorods

Herein, a facile low temperature, aqueous solution-based chemical method has been demonstrated for large-scale fabrication of Fe doped ZnO nanorods (ZnO:Fe) with a series percentage of Fe dopant. Interestingly, the SEM results reveal a uniform well dispersed synthesis of ZnO:Fe nanorods throughout the substrate. The x-ray diffraction result suggests that Fe substitutes Zn in the ZnO matrix and rules out the formation of any secondary phase. Selected area electron diffraction investigation verifies the single crystal, hexagonal wurtzite structure of the ZnO:Fe nanorods. Energy dispersive spectroscopy data confirm Fe doping of the ZnO nanorods with a concentration ranging from 0.9 to 2.2 at.%. The photoluminescence spectrum reveals a continuous suppression of defect related broad-band emission (I(D)/I(UV) = 1-0.11) by increasing the concentration of the dopant ion, which produces the quenching of surface defects present in the nanostructures. An enhancement in ferromagnetism (M = 0.15 × 10?2-0.24 × 10?1 emu g?1 at 2000 Oe) is found in doped ZnO nanorods.     

ZnO nanostructure thin films by continuous spray pyrolysis using doped precursor for Si solar cell application

This work presents deposition of Zn solution seed layer assisted growth of zinc oxide (ZnO) nanostructure layers by continuous spray pyrolysis reactor using lanthanides (Er and Eu) and metal (Al) influenced zinc acetate precursor solution. Dopants in precursors have influenced structural property, surface morphology and optical reflectance of resulting ZnO thin films which are supported by X-ray diffractometer, scanning electron microscope and reflectance measurements. Enhanced dispersion amongst nanorods is observed under the influence of Er and Al dopant in ZnO thin film. The change of precursor from Zinc acetate to Titanium tetraisopropoxide for Er doped precursor is helping to achieve better crystalline ZnO nanorods arrangement with increased homogenous growth, which results into improved light reflectance reduction of thin film. The experimental evidences of light reflectance from ZnO nanorods on Si surface is studied with the help of FDTD based Lumerical software package which can be a useful study for designing ZnO nanorods thin film in device purposes. The utility of ZnO layer by this reactor on low efficiency Si solar cell is also explored in improving device efficiency via increase of photocurrent.