Synthesis and characterization of ZnO-Ag core-shell nanocomposites with uniform thin silver layers

This paper presents an investigation on the synthesis and characterization of ZnO-Ag core-shell nanocomposites. ZnO nanorods were employed as core material for Ag seeds, and subsequent nucleation and growth of reduced Ag by formaldehyde formed the ZnO-Ag core-shell nanocomposites. The ZnO-Ag nanocomposites were annealed at different temperature to improve the crystallinity and binding strength of Ag nanoparticles. The morphology, microstructure and optical properties of the ZnO-Ag core-shell nanocomposites were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, ultraviolet-visible (UV-vis) absorption and photoluminescence measurement. It was demonstrated that very small face-center-cubic Ag nanoparticles were coated on the surface of ZnO nanorods. The ultraviolet absorption and surface plasmon absorption band of ZnO-Ag core-shell nanocomposites exhibited some redshifts relative to pure ZnO nanorods and monometallic Ag nanoparticles. The coating of Ag nanocrystals onto the ZnO nanorods completely quenched the photoluminescence. These observations reflected the strong interfacial interaction between ZnO nanorods and Ag nanoparticles. The effect of Ag coating thickness on the morphology and optical properties of ZnO-Ag core-shell nanocomposites was also investigated. Moreover, the growth mechanism of ZnO-Ag core-shell nanocomposites was also proposed and discussed in detail.     

Controllable synthesis of Ag nanorods using a porous anodic aluminum oxide template

This paper describes a new approach to the synthesis of Ag nanorods. A solvothermal method was used to make Ag nanoparticles inside anodic aluminum oxide (AAO) templates. The nanoparticles were then annealed at 300 °C to produce Ag nanorods. The size of AAO templates, which is focused on in this study, would determine the diameter of Ag nanorods. The product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In this study, a nanorod growth mechanism is deduced, and understanding of the growth of nanorods inside AAO templates is furthered. This work demonstrates that it is possible to make crystalline nanorods that the size can be varied.     

Growth and optical study of ZnO nanorods

ZnO nanorods were grown by a simple near room temperature, chemical solution method on ZnO-seeded silicon substrates. Study of the ZnO nanorods over different growth times by electron microscopy methods revealed that the resulting ZnO nanorods were single crystalline with a highly preferential growth perpendicular to the substrate and a very good c-axis alignment. The size of the nanorods increased with increasing growth time. The growth mechanism is briefly discussed. Post-annealing in oxygen slightly improved the surface roughness of the ZnO nanorods. Photoluminescence experiments at 1.6 K revealed a major emission peak of the nanorods at around 3.36 eV which is attributed to the band edge transition of ZnO, while defect-related emission is relatively weak.     

Amplification of raman scattering by localized plasmons in silver nanoparticles on the surface of zinc oxide nanorods

The magnetron sputtering of Ag nanoparticles onto ZnO nanorod arrays is studied. The lateral faces of the nanorods are coated with nanoparticles at a much lower density as compared to the flat faces at comparable sputtering times. The silver density is high on the edges of the lateral faces of the nanorods. The plasmon absorption in the synthesized arrays of nanorods coated with individual Ag nanoparticles is maximal at 450?C500 nm. The appearance of local plasmon excitations increases the intensity of the multiphonon processes with the participation of ZnO polar modes in Raman spectra. The cross section of resonance Raman scattering for A ₁(LO) phonon overtones increases with the equivalent Ag film thickness.     

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.     

Growth of ZnO nanorods by a simple chemical method

ZnO nanorods were grown by a near-room-temperature, simple, chemical solution method on large-area Zn foils and substrate materials such as silicon, and zinc oxide thin films on silicon and glass. Study of the ZnO nanorods on the different substrates by electron microscopy methods shows that the morphology and size of the ZnO nanorods can be tuned varying the growth parameters and the substrates used. The growth mechanism is briefly discussed. Photoluminescence experiments at room temperature reveal a major emission peak of the nanorods at around 385 nm, which is attributed to the band edge transition of ZnO and weaker defect-related visible band peaks. PACS 81.05.Dz; 78.55.Et; 81.07.-b     

Defect-dominated optical emission and enhanced ultraviolet photoconductivity properties of ZnO nanorods synthesized by simple and catalyst-free approach

We report on the defect-dominated light emission and ultraviolet (UV) photoconductivity characteristics of ZnO nanorods (NRs) fabricated using a facile, cost-effective, and catalyst-free thermal decomposition route under varying reaction temperatures. The morphological and structural studies reveal the formation of homogeneous quality nanorods in large scale at the highest reaction temperature of 600 ^°C. The luminescence feature of the nanorods is dominated by the defect related emission over the typical band edge emission. The variation of band-edge and native defect-related emission response of the samples has been correlated to the morphology and microstructure. In photoconductivity studies, the I–V characteristics of the ZnO NRs prepared at different reaction temperatures in dark and under UV illumination (λ=365 nm) follow the power law, i.e., IαV ^r . An enhanced ultraviolet photodetection has been observed in the nanorods fabricated at the highest reaction temperature of 600 ^°C. The sample prepared at highest reaction temperature of 600 ^°C exhibits UV photosensitivity value (photo-to-dark current ratio) of around 1.18×10³, which is much higher in magnitude compared to that of the samples prepared at lower reaction temperatures. The enhanced photoconductivity may be assigned to the development of uniformity and homogeneity of the nanorods. Further development of such ZnO nanostructures can form the basis of promising prototype luminescent and UV photodetecting devices.     

Field emission characteristics study for ZnO/Ag and ZnO/CNTs composites produced by DC electrophoresis

A simple controllable method is reported for the coating of ZnO nanowires with Ag nanoparticles and ZnO/carbon nanotubes (CNTs) composite. It has been achieved through DC electrophoresis AgNO₃ electrolyte and CNTs in the presence of isopropanol dispersion of ZnO nanowires. In the present work, the influence of Ag nanoparticles and CNTs on the field emission properties of the composite materials is studied. The results of this research demonstrate a remarkable enhancement of field emission current of ZnO nanowires in case of CNTs mixture and Ag nanoparticles coating.     

Microstructure and photoluminescence of MoOx decorated ZnO nanorods

Various MoO_x decorated ZnO nanorods (ZnO-MoO_x) samples were fabricated by physical vapor deposition of MoO_x on the surface of ZnO nanorods with varying deposition time and temperature. The microstructure and photoluminescence (PL) of the ZnO-MoO_x samples were investigated. It was found that the morphology of the ZnO nanorods is changed from hexagonal prisms to lotus-roots-like shapes by the decoration of MoO_x. The lotus-roots-like shapes may be formed by partial melting and evaporating of ZnO-MoO_x during the MoO_x decoration. This result shows that one can use the thermal instability of a nano-material to obtain an interesting structure, although a thermal instability should often be avoided. The intensity of the ultraviolet and visible light emission the of ZnO nanorods have different dependencies on the MoO_x decoration. Although the position of the ultraviolet light emission is not obviously changed by the MoO_x decoration, the ultraviolet light emission intensity is greatly weakened. In contrast, the intensity and position of visible light emission is largely changed. The blue shift of the visible light emission might be related to defects introduced by melting of the ZnO nanorods.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

掺银氧化锌纳米棒的水热法制备研究

利用水热法在直流磁控溅射制备的掺铝氧化锌 (AZO) 种子层上制备了不同形貌和光学性能的掺银ZnO纳米棒, 并采用XRD、扫描电镜、透射谱、光发射谱和EDS谱详细研究了Ag离子与Zn离子的摩尔百分比 (R_Ag/Zn) 及AZO种子层对掺银ZnO纳米棒的结构和光学性质的影响. 随着R_Ag/Zn的增加, 掺银ZnO 纳米棒的微结构和光学性质的变化与银掺杂诱导的纳米棒的端面尺寸变化有关. 平均端面尺寸的变化归结于种子层颗粒大小和颗粒数密度不同导致掺入的Ag离子的相对比例不同. 溅射15 min的AZO种子层上生长的ZnO纳米棒由于缺陷增多导致在可见光区的发光峰明显强于溅射10 min 的AZO种子层上、相同R_Ag/Zn 条件下生长的ZnO纳米棒. Ag掺杂产生的点缺陷增多导致可见光区PL波包较宽. 纯ZnO纳米棒的微结构与种子层厚度导致的结晶度和颗粒大小有关. 关键词： ZnO纳米棒 水热法 Ag掺杂 直流磁控溅射     

Significant Fowler–Nordheim tunneling across ZnO – Nanorod based nanojunctions for nanoelectronic device applications

We demonstrate significant Fowler–Nordheim (FN) tunneling across Al/Al₂O₃/ZnO metal–insulator–semiconductor (MIS) and Ag/ZnO metal–semiconductor (MS) nanojunctions. The transport properties of ZnO nanostructures in the form of urchins and randomly distributed nanorods were investigated in terms of various conduction mechanism. The minimum voltage necessary for triggering Fowler–Nordheim (FN) tunneling, under forward biasing, was ～1.2 V and ～3.4 V; respectively, below which only direct tunneling and thermionic emission events were evident. Mediated through Al₂O₃ layer, the FN tunneling was more prominent across MIS junction than MS one. The weak FN tunneling across MS junction was owing to interfacial charge transfer process through the atomic scale gapping between adjacent nanostructures. The extent of such type of tunneling is found to be nanostructure morphology dependent and largely rely on the free electrons donated by the native donor defects in the crystal structure of ZnO. The significant FN tunneling across the MIS and MS junctions has a direct relevance in designing nanoscale field emission devices/components working at low voltage with high throughputs.     

Site‐specific deposition of Ag nanoparticles on ZnO nanorod arrays via galvanic reduction and their SERS applications

A controllable heterostructure consisting of ZnO nanorod arrays with attached Ag nanoparticles at only one end has been synthesized via a facile and convenient galvanic reduction method. Scanning electron microscopic images of these nanostructures showed good selectivity of Ag deposition on the tip of ZnO nanorod arrays. The formation of these regular Ag ZnO heterogeneous nanorod arrays can be explained by a localization of the electrons at the ends of the ZnO nanorods after the electron transfer step. By tuning the reaction time and the concentration of silver nitrate, the density of Ag nanoparticles on the tip of ZnO nanorods can be well controlled. Owing to the introduction of Ag nanoparticles with different densities, the resulting Ag ZnO heterogeneous nanorod arrays have been proved to be a versatile substrate for surface‐enhanced Raman scattering not only for common organic molecules but also for label‐free protein detection. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies of luminescence properties of ZnO and ZnO:Zn nanorods prepared by solution growth technique

Pyramidal ZnO nanorods with hexagonal structure having c-axis preferred orientation are grown over large area silica substrates by a simple aqueous solution growth technique. The as-grown nanorods were studied using XRD, SEM and UV-vis photoluminescence (PL) spectroscopy for their structural, morphological and optical properties, respectively. Further, the samples have also been annealed under different atmospheric conditions (air, O₂, N₂ and Zn) to study the defect formation in nanorods. The PL spectra of the as-grown nanorods show narrow-band excitonic emission at 3.03 eV and a broad-band deep-level emission (DLE) related to the defect centers at 2.24 eV. After some mild air annealing at 200 °C, fine structures with peaks having energy separation of ∼100 meV were observed in the DLE band and the same have been attributed to the longitudinal optical (LO) phonon-assisted transitions. However, the annealing of the samples under mild reducing atmospheres of N₂ or zinc at 550 °C resulted in significant modifications in the DLE band wherein high intensity green emission with two closely spaced peaks with maxima at 2.5 and 2.7 eV were observed which have been attributed to the V_O and Zn_i defect centers, respectively. The V-I characteristic of the ZnO:Zn nanorods shows enhancement in n-type conductivity compared to other samples. The studies thus suggest that the green emitting ZnO:Zn nanorods can be used as low voltage field emission display (FED) phosphors with nanometer scale resolution.     

金纳米颗粒等离激元对不同形貌氧化锌薄膜发光性能的调控

采用化学气相沉积法制备了纳米棒状的氧化锌纳米结构薄膜和没有纳米棒的氧化锌薄膜,通过直流溅射在所制备的有纳米棒和没有纳米棒的氧化锌薄膜上淀积约3 nm厚的金纳米颗粒薄膜,研究了金纳米颗粒对不同表面形貌氧化锌薄膜的发光特性的影响。实验发现金纳米颗粒的存在使具有纳米棒的氧化锌薄膜的紫外发射增强,但使来自缺陷的可见光发射受到很大的抑制。通过比较有纳米棒和没有纳米棒的氧化锌薄膜在镀金纳米颗粒前后的发光特性,发现金表面等离激元对氧化锌发光的调控取决于氧化锌的表面形貌,纳米棒的存在更有利于金纳米颗粒等离激元调控氧化锌的发光特性。     

Al和Sb共掺对ZnO有序阵列薄膜的结构和光学性能的影响

采用水热合成法在预先生长的ZnO种子层的玻璃衬底上制备出Al和Sb共掺ZnO纳米棒有序阵列薄膜. 通过X射线衍射、扫描电镜、透射电镜和选区电子衍射分析表明:所制备的薄膜由垂直于ZnO种子层的纳米棒组成, 呈单晶六角纤锌矿ZnO结构, 且沿[001]方向择优生长, 纳米棒的平均直径和长度分别为27.8 nm和1.02 μm. Al和Sb共掺ZnO纳米棒有序阵列薄膜的拉曼散射分析表明:相对于未掺杂ZnO薄膜的拉曼振动峰(580 cm^-1), Al和Sb共掺ZnO阵列薄膜的E₁(LO)振动模式存在拉曼位移. 当Al和Sb的掺杂量为3.0at%,4.0at%,5.0at%,6.0at%时, Al和Sb共掺ZnO阵列薄膜的拉曼振动峰的位移量分别为3,10,14,12 cm^-1. E₁ (LO) 振动模式位移是由Al和Sb掺杂ZnO产生的缺陷引起的. 室温光致发光结果表明:掺杂Al和Sb后, ZnO薄膜在545 nm处的发光强度减小,在414 nm处的发光强度增加. 这是由于掺杂Al和Sb后, ZnO薄膜中Zn_i缺陷增加, O_i缺陷减少引起的. 关键词： Al和Sb共掺ZnO薄膜 纳米棒有序阵列 结构表征 拉曼散射     

Enhancement of optical properties and donor-related emissions in Y-doped ZnO

The Zn_1−xY_xO nanoparticles with good optical properties have been prepared by sol–gel method. The yttrium doping effect on the structures and optical properties were investigated by XRD, SEM, XPS and low temperature photoluminescence. The UV emission intensity of yttrium doped ZnO was over 300 times stronger than that of pure ZnO, which was an exciting result in enhancing the ultraviolet near band edge emission in photoluminescence from ZnO nanoparticles. The UV emission band of doped ZnO nanoparticles exhibits a red shift from 388 to 398 nm, indicating a shallow energy level near valence band has been formed due to the yttrium doping into ZnO lattices. The defect-related band is suppressed (I_D/I_UV = 1–0.83) considerably in Zn_1−xY_xO nanoparticles, revealing the quenching of the broad yellow-orange emission. The doping effect on the optical properties is investigated by temperature dependent photoluminescence. The experimental results indicated that the donor level of yttrium is deeper than that of undoped ZnO.     

The effect of Al doping on the morphology and optical property of ZnO nanostructures prepared by hydrothermal process

The undoped and Al-doped ZnO nanostructures were fabricated on the ITO substrates pre-coated with ZnO seed layers using the hydrothermal method. The undoped well-aligned ZnO nanorods were synthesized. When introducing the Al dopant, ZnO shows various morphologies. The morphology of ZnO changes from aligned nanorods, tilted nanorods, nanotubes/nanorods to the nanosheets when the Al doping concentrations increase. The ZnO nanostructures were characterized by X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence and Raman technology. The Al doping concentrations play an important role on the morphology and optical properties of ZnO nanostructures. The possible growth mechanism of the ZnO nanostructures was discussed.     

Morphological transition of ZnO nanostructures influenced by magnesium doping

Wurtzite zinc oxide (ZnO) nanochains have been synthesized through high-pressure pulsed laser deposition. The chain-like ZnO nanostructures were obtained from magnesium (Mg) doped ZnO targets, whereas vertically aligned nanorods were obtained from primitive ZnO targets. The Mg doping has influenced the morphological transition of ZnO nanostructures from nanorods to nanochains. The field emission scanning electron microscope images revealed the growth of beaded ZnO nanochains. The ZnO nanochains of different diameters 40 and 120 nm were obtained. The corresponding micro-Raman spectra showed strong E_2H mode of ZnO, which confirmed the good crystallinity of the nanochains. In addition to near band edge emission at 3.28 eV, ZnO nanochains show broad deep level emission at 2.42 eV than that of ZnO nanorods.     

Spontaneous organisation of ZnS nanoparticles into monocrystalline nanorods with highly enhanced dopant-related emission

A natural self-assembly process of semiconductor nanoparticles leading to the formation of doped, monocrystalline nanorods with highly enhanced dopant-related luminescence properties is reported. ∼4 nm sized, polycrystalline ZnS nanoparticles of zinc-blende (cubic) structure, doped with Cu⁺-Al³⁺ or Mn²⁺ have been aggregated in the aqueous solution and grown into nanorods of length ∼400 nm and aspect ratio ∼12. Transmission electron microscopic (TEM) images indicate crystal growth mechanisms involving both Ostwald-ripening and particle-to-particle oriented-attachment. Sulphur-sulphur catenation is proposed for the covalent-linkage between the attached particles. The nanorods exhibit self-assembly mediated quenching of the lattice defect-related emission accompanied by multifold enhancement in the dopant-related emission. This study demonstrates that the collective behavior of an ensemble of bare nanoparticles, under natural conditions, can lead to the formation of functionalized (doped) nanorods with enhanced luminescence properties.