Synthesis of dimension-tunable ZnO nanostructures via the design of zinc hydroxide precursors

A facile synthesis route is presented to achieve dimension-tunable ZnO nanostructures by the design of zinc hydroxide precursors under the surfactant-free condition. From three types of zinc hydroxide precursors, namely, crystalline Zn(OH)(NO₃)(H₂O) nanobelts, amorphous zinc hydroxides microparticles and soluble Zn(OH)^2-₄\mathrm{Zn}(\mathrm{OH})^{2-}_{4} species, the porous ZnO nanosheets, ZnO nanoparticles and ZnO nanowires can be achieved, respectively. The porous ZnO nanosheets exhibit large polar surface area. Thermal analysis indicates that the crystalline Zn(OH)(NO₃)(H₂O) nanobelts were converted to the porous ZnO nanosheets by in situ lattice reconstruction, which was attributed to the unique fibrous structure of Zn(OH)(NO₃)(H₂O) nanobelts. The as-prepared dimension-tunable ZnO nanostructures have potential applications in solar cells, photocatalysis, novel chemical and biological sensors, etc.     

Effect of zinc nitrate concentration on the structural and the optical properties of ZnO nanostructures

ZnO nanorods and nanodisks were formed on indium-tin-oxide-coated glass substrates by using an electrochemical deposition method. Scanning electron microscopy images showed that the ZnO nanorods were transformed into nanodisks with increasing Zn(NO₃)₂ concentration. X-ray diffraction patterns showed that the ZnO nanostructures had wurzite structures. The full widths at half maxima of the near band-edge emission peak of photoluminescence spectra at 300 K for ZnO nanorods were small, indicative of the high quality of the nanorods. These results indicate that the structural and the optical properties of ZnO nanostructures vary by changing Zn(NO₃)₂ concentration.     

ZnO spheres and nanorods formation: their dependence on agitation in solution synthesis

ZnO nanostructures including nanorods, dense, and partially hollow spheres were synthesized via a solution synthesis method with temperature ranging from 65 to 95 °C. Scanning electron microscopy (SEM) revealed that the diameter of the spheres is in the range of 200–500 nm. Transmission electron microscopy (TEM) showed that some of the spheres are hollow or partially hollow. Powder X-ray Diffraction (XRD) and TEM-Selected area electron diffraction (SAED) analysis showed that the spheres consist of polycrystalline nanoparticles. It was found for the first time that the agitation during the synthesis plays a critical role on morphology of the ZnO nanostructures formed in solution. The oriented attachment of nanocrystals without agitation during the synthesis could guide the nanocrystals to form an ordered nanorod structure. However, the disordered aggregation of the nanocrystals under shear force resulted in a spherical morphology. It was also found that the composition of spheres is different from that of nanorods: the spheres consist of both ZnO and Zn(OH)₂, but nanorods consist of single-crystal ZnO only. Zn(OH)₂ presented in the spheres could decompose to ZnO by calcination, resulting in the formation of hollow spheres.     

Effect of ultrasonic treatment before and after hydrothermal process on the morphologies and formation mechanism of ZnO nanorods

ZnO nanorods were fabricated by ultrasonic treatment before and after a hydrothermal process. The morphology and structure of the nanorods were individually characterized by scanning electron microscopy and X-ray diffraction. The results show that before the hydrothermal process, fore-ultrasonic treatment can directly gain ZnO nanorods which mainly experienced four conversion stages from initial bulk Zn(OH)₂, a coexisting phase of bulk Zn(OH)₂ with ZnO nanoslices, ZnO nanoslices with flower-like ZnO nanorods and finally to purely flower-like ZnO nanorods. After the hydrothermal process, the post-ultrasonic treatment mainly influences the aggregation degree of the ZnO nanorods. The formation mechanism of ultrasonic treatment on ZnO nanorods is also discussed.     

40% Efficiency enhancement in solar cells using ZnO nanorods as shell prepared via novel hydrothermal synthesis

Herein, rod-like ZnO nanostructures were synthesized via a novel hydrothermal route using Zn(OAc)₂, ethylenediamine and hydrazine as a new set of starting reagents. The as-synthesized products were characterized by techniques including XRD, EDS, SEM, XPS, Pl and FTIR. The prepared ZnO nanostructures were utilized as shell on TiO₂ film in DSSCs. Effect of precursor type, morphology and thickness of ZnO shell (number of electrophoresis cycle) on solar cells efficiency were well studied. Our results showed that ethylenediamine has crucial effect on morphology of synthesized ZnO nanostructures and using ZnO nanostructures leads to an increase in DSSCs efficiency compared to bare TiO₂ from 4.66 to 7.13% (~40% improvement). Moreover, highest amount of solar cell efficiency (7.13%) was obtained by using ZnO nanorods with two cycle of electrophoresis for deposition.     

The growth mechanism of ZnO single-crystal nanorods synthesized by polymer complexing with zinc salts

The growth mechanism of single-crystal ZnO nanorods synthesized by the method of polymer complexing with zinc salts is investigated. The annealing temperature is controlled at about the decomposition temperature of dihydrate zinc acetate (Zn(O₂CCH₃)₂·2H₂O) of 573 K. By changing the annealing time, the ZnO nanostructures can be modified from nanoparticles to nanorods. As a result, the formation of single-crystal ZnO nanorods can be observed. Through investigating the Fourier transform infrared spectra of (a) polyvinyl pyrrolidone (PVP), (b) Zn(O₂CCH₃)₂·2H₂O and (c) the mixture of PVP and Zn(O₂CCH₃)₂(H₂O)₂, the interaction between PVP and Zn(O₂CCH₃)₂·2H₂O can be observed. PVP plays an important role in the growth of the single-crystal ZnO nanorods. We analyze the growth process of ZnO nanorods by observing their TEM images at different moments. Consequently, our results indicate that the single-crystal ZnO nanorods were formed by self-assembling the ZnO nanoparticles. PACS 61.46.Hk; 61.46.Df; 78.30.-j; 81.07.-b; 81.16.Be     

Self-assembled 3D La(OH)3 and La2O3 nanostructures: Fast microwave synthesis and characterization

Self-assembled three-dimensional (3D) urchin-like and flower-like La(OH)₃ nanostructures were successfully prepared for the first time via a facile and fast microwave-assisted solution-phase chemical method in 15 min. The obtained products were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The SEM results reveal that the urchin-like and flower-like La(OH)₃ nanostructures are ca. 3 μm and 6 μm in diameter, respectively. The urchin-like La(OH)₃ nanostructures are constructed by nanorods with diameters of about 300 nm and lengths of about 500 nm. The flower-like La(OH)₃ nanostructures are built from nanopetals about 100 nm thick. The effects of reaction time, microwave power, amount of tetraethyl ammonium bromide (TEAB), and surfactants on the preparation were systematically investigated. The possible formation mechanism of the 3D La(OH)₃ nanostructures was preliminarily discussed. Urchin-like and flower-like La₂O₃ nanostructures were obtained after calcining the La(OH)₃ nanostructures at 800 °C for 4 h. Urchin-like and flower-like La₂O₃:Eu³⁺ nanostructures were also prepared and their photoluminescence (PL) properties were investigated.     

Synthesis of ZnO nanostructures with controlled morphology and size in ionic liquids

Nanostructured ZnO has been synthesized by a hydrothermal route, using different ionic liquids (ILs) as the morphology templates. The morphology of ZnO changes from rod-like to star-like and flower-like in different ILs. A 3D nano/micro structure ZnO with unique flower-like morphology has been synthesized via the assembly of dicationic IL and [Zn(OH)₄]²⁻. The flower-like pattern was obtained in the presence of IL 1. The flower-like ZnO structure has a hexagonal prism, with a hexagonal pyramid on the tip, and diameter of ~444 nm. While the ZnO prepared in IL 2, shows uniform rod-like shape with a diameter of 91 nm, star-like morphology consisting of nanorods with diameter of ~109 nm was formed in IL 3. The XRD, SEM, and PL spectra have been employed for characterization of the synthesized ZnO nano structures.     

Zn-catalyzed growth processes and ferromagnetism of Mn-doped ZnO nanorods on Si substrate

Well-aligned ZnO nanorods and Mn-doped ZnO nanorods are fabricated on Si (1 0 0) substrate according to the contribution of Zn metal catalysts. Scanning electron microscopy and high-resolution transmission electron microscopy images indicate that the influence of Zn catalyst on the properties of ZnO can be excluded and the growth of ZnO nanorods follows a vapor-liquid-solid and self-catalyzed model. Mn-doped ZnO nanorods show a typical room temperature ferromagnetic characteristic with a saturation magnetization (M_S) of 0.273μ_B/Mn. Cathodoluminescence suggests that the ferromagnetism of Mn-doped ZnO nanorods originates from the Mn²⁺-Mn²⁺ ferromagnetic coupling mediated by oxygen vacancies. This technique provides exciting prospect for the integration of next generation Si-technology-based ZnO spintronic devices.     

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.     

Evolution of the zinc compound nanostructures in zinc acetate single-source solution

A series of nanostructured zinc compounds with different nanostructures such as nanobelts, flake-like, flower-like, and twinning crystals was synthesized using zinc acetate (Zn(Ac)₂) as a single-source. The evolution of the zinc compounds from layered basic zinc acetate (LBZA) to bilayered basic zinc acetate (BLBZA) and twinned ZnO nano/microcrystal was studied. The low-angle X-ray diffraction spectra indicate the layered spacing is 1.34 and 2.1 nm for LBZA and BLBZA, respectively. The Fourier transform infrared (FTIR) spectra results confirmed that the bonding force of acetate anion with zinc cations decreases with the phase transformation from Zn(Ac)₂ to BLBZA, and finally to LBZA. The OH⁻ groups gradually replaced the acetate groups coordinated to the matrix zinc cation, and the acetate groups were released completely. Finally, the Zn(OH)₂ and ZnO were formed at high temperature. The conversion process from Zn(Ac)₂ to ZnO with release of acetate anions can be described as Zn(Ac)₂ → BLBZA → LBZA → Zn(OH)₂ → ZnO.     

Vapour transport growth of ZnO nanorods

The fabrication of low-dimensional ZnO structures has attracted enormous attention as such nanostructures are expected to pave the way for many interesting applications in optoelectronics, spin electronics gas sensor technology and biomedicine. Many reported fabrication methods, especially for ZnO nanorods are mostly based on catalyst-assisted growth techniques that employ metal-organic sources and other contaminating agents like graphite to grow ZnO nanorods at relatively high temperatures. We report on catalyst-free vapour-phase epitaxy growth of ZnO nanorods on 6H-SiC and (11-20)Al₂O₃ using purely elemental sources at relatively low temperatures and growth pressure. ZnO nanorods with widths of 80–900 nm and lengths of up to 12 μm were obtained. Nanorod density on the order of 10⁹ cm^-2 with homogenous luminescence and high purity was also noted. PACS 81.10.Bk; 81.15.Kk; 81.16.Hc; 78.55.Et; 81.05.Dz; 81.07.Bc     

Synthesis, characterization and photoluminescent properties of rare-earth hydroxides and oxides nanorods by hydrothermal route

The stable and crystalline pure phase Ln(OH)₃ (Ln=La, Nd, Sm, Eu, Gd, Tb, and Dy) nanorods are synthesized by a facile hydrothermal method using the simple chemical materials (rare-earth chloride hexahydrate LnCl₃?6H₂O and NH₃?H₂O) and polymer polyvinypyrrolidone (PVP). The as-prepared Ln(OH)₃ nanorods can be successfully converted to Ln₂O₃ nanorods via calcination under appropriate conditions. X-ray diffraction (XRD) spectra, Fourier transformed infrared (FTIR) spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-Resolution TEM (HRTEM), and Raman spectroscopy were used to examine the morphologies and microstructures to find out the cause. The analyzed results indicate that the obtained nanorods are rare-earth hydroxides and oxides with 1D nanostructures. The formation mechanism of the Ln(OH)₃ and Ln₂O₃ nanorods was investigated. Optical properties of the Ln(OH)₃ and Ln₂O₃ nanorods were determined by photoluminescence (PL). Ln(OH)₃ and Ln₂O₃ nanorods exhibit a strong blue emission with the strongest narrow bands at about 469 nm corresponding to the intra-4f transitions ⁵D₂→⁷F₆, which have potential applications in fluorescent devices.     

Controlled hydrothermal growth of ZnO nanostructures by sequestering the Zn metal ions with the chelating agent EDTA

In the present work, a controlled growth of ZnO nanostructures by manipulating Zn metal ion concentration by the chelating action of ethylene diaminetetra acetic acid in hydrothermal method is studied. EDTA produces metal–chelate complex by the formation of bidentate ligand with Zn²⁺ in the solution and diminishes the reactivity of Zn metal cations. Concentration of EDTA in the mother solution was varied in different ranges like 3, 5 and 10 mM while retaining the zinc metal salt and the NaOH concentration the same. Three different morphologies of wurtzite structured ZnO nanostructures such as nanorods-bunch, separate/discrete uniformly sized hexagonal nanorods and tapered flower petals like shapes are achieved by 3, 5 and 10 mM strengths of EDTA, respectively. The medium concentration 5 mM of EDTA is found to have moderate control over producing ZnO nanostructures of uniform diameter and a high aspect (length to diameter) ratio. An array of vertically aligned free standing ZnO nanorods with uniform spacing is successfully achieved by the addition of 5 mM of EDTA in the mother solution and the same is studied for its fluorescence property at an excitation of 325 nm and it has exhibited a characteristic UV emission of ZnO around 383 nm.     

Fabrication and characterization of ZnO micro and nanostructures prepared by thermal evaporation

A simple method of thermal evaporation to fabricate micro and nanostructures of zinc oxide was presented. ZnO micro and nanostructures, prepared under different quantity of O₂, were characterized by techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and analytical transmission electron Microscope. The SEM images indicated that the products prepared under the condition of sufficient O₂ were needle-like microrods and the samples synthesized under the condition of deficient O₂ were nanorods and nanowires with very high aspect ratio. The results of XRD and Raman shifts revealed that the ZnO micro and nanostructures synthesized under different quantity of O₂ were both single crystalline with the hexagonal wurtzite structure. The HRTEM images indicated that the ZnO nanowire prepared under the condition of deficient O₂ was single crystalline and grown along the direction of [0 0 1]. Photoluminescence measurement was carried out and it showed that the spectra of ZnO micro and nanostructures prepared under different quantity of O₂ exhibited similar emission features. In addition, the growth mechanism of ZnO micro and nanostructures was preliminarily discussed.     

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.     

Reductive hydrothermal synthesis of La(OH)<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript> nanorods as a new green emitting phosphor

A reductive hydrothermal process with use of hydrazine hydrate as a protecting agent is proposed to synthesize La(OH)₃:Tb³⁺ (Tb mol% = 0, 1, 5, 10, and 20) nanorods. The oxidation of Tb³⁺−Tb⁴⁺ was effectively prevented in the presence of hydrazine hydrate; hence the La(OH)₃:Tb³⁺ nanorods exhibited much stronger green photoluminescence than the product prepared by the normal hydrothermal process. X-ray diffraction and transmission electron microscopy were employed to characterize the products, the results of which revealed that all the products were one-dimensional rod-like nanostructures of hexagonal structure (∼20 nm in diameter). The reductive hydrothermal process is desirable for the synthesis of other efficient Tb³⁺ doped nanophosphers.     

Enhanced ethanol sensing properties of TiO2/ZnO core–shell nanorod sensors

TiO₂-core/ZnO-shell nanorods were synthesized using a two-step process: the synthesis of TiO₂ nanorods using a hydrothermal method followed by atomic layer deposition of ZnO. The mean diameter and length of the nanorods were ～300 nm and ～2.3 μm, respectively. The cores and shells of the nanorods were monoclinic-structured single-crystal TiO₂ and wurtzite-structured single-crystal ZnO, respectively. The multiple networked TiO₂-core/ZnO-shell nanorod sensors showed responses of 132–1054 % at ethanol (C₂H₅OH) concentrations ranging from 5 to 25 ppm at 150 ^°C. These responses were 1–5 times higher than those of the pristine TiO₂ nanorod sensors at the same C₂H₅OH concentration range. The substantial improvement in the response of the pristine TiO₂ nanorods to C₂H₅OH gas by their encapsulation with ZnO may be attributed to the enhanced absorption and dehydrogenation of ethanol. In addition, the enhanced sensor response of the core–shell nanorods can be attributed partly to changes in resistance due to both the surface depletion layer of each core–shell nanorod and the potential barriers built in the junctions caused by a combination of homointerfaces and heterointerfaces.     

Controlled synthesis of oriented ZnO nanorod arrays by seed-layer-free electrochemical deposition

Oriented ZnO nanorod arrays were successfully prepared on transparent conductive substrates by seed-layer-free electrochemical deposition in solution of Zn(NO₃)₂ at a low temperature of 70 °C without using any catalysts, additives, and additional seed crystals. The effects of the Zn(NO₃)₂ concentration, deposition time and applied current on the localized nanorod arrays are investigated. X-ray powder diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) were used to characterize the structures and the morphologies of ZnO nanorod arrays. The heights and diameters of ZnO nanorods can be tuned by controlling the electrodeposition parameters.     

Synthesis, morphology and random laser action of ZnO nanostructures

Three-dimensional (3-D) ZnO random-wall nanostructures and one-dimensional (1-D) ZnO nanorods were prepared on silicon substrates by a simple solid-vapour phase thermal sublimation technique. Optical pumped random lasing has been observed in the ZnO random-wall arrays with a threshold intensity of 0.38 MW/cm² in the emission wavelength from 380 to 395 nm. The optical gain was attributed to the closed-loop scattering and light amplification of the ZnO random-wall. The experimental result suggests that the morphology of nanostructure is the key factor to effect random lasing.